TW200535098A - Oxide solid solution powder - Google Patents
Oxide solid solution powder Download PDFInfo
- Publication number
- TW200535098A TW200535098A TW094101641A TW94101641A TW200535098A TW 200535098 A TW200535098 A TW 200535098A TW 094101641 A TW094101641 A TW 094101641A TW 94101641 A TW94101641 A TW 94101641A TW 200535098 A TW200535098 A TW 200535098A
- Authority
- TW
- Taiwan
- Prior art keywords
- oxide
- solid solution
- abrasive
- mass
- grinding
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/229—Lanthanum oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
200535098 九、發明說明: 【發明所屬之技術領域】 本發明係關於氧化物固溶體,特別係關於以^ 卜 稀土族氧化物作為主成分之氧化物固溶體的粉末。 寻 【先前技術】 氧化鈽等稀土族氧化物係使用於研磨材、觸媒擔體、 紫外線吸收劑等各種用途。例如以氧化鈽作為主成分之稀 土族氧化物已知係適宜作為研磨材,可使用來作為以光碟 用^磁碟用、1XD用、HD狀玻璃基㈣為首之玻璃材料 2研磨材。繼而,在以使用如上述之玻璃基板的電子機哭 ^造領域為首,並使用研磨材之各領域中,係尋求研磨^ 精度向之研磨材(稀土族氧化物)。 在如上述之領域所使用的研磨材,係例如有··當研磨 材浆液調製時,在含氧化鈽之氟碳鈽鑛(bastnaesite)系ς 磨材中混合氟化鈽與硫酸赶,進一步混合水所得到之製液 研磨材(參照專利文獻υ。藉在漿液中存在㈣子,欲防 止在漿液中之粒子的沈殺或研磨塾之堵塞而避免研磨損傷 的發生。 其他亦有例如於研磨材的主原料之稀土族碳酸鹽與稀 /矢乳化物中,在研磨材製造時之培燒步驟前混合氯化 、巧二後進订培燒所製造的研磨材(參照專利文獻2)。若 :燒前混合氯化舞’可抑制培燒時之異常粒成長,很容易 ;空制培燒時之粒子平均粒徑或粒徑分布,可更容易地製造 平句粒仫小的研磨材。此結果,即使不含氟成分,亦可製 3J6680 200535098 造避免研磨面精度降低之研磨材。 (專利文獻1)特開平6-330025號公報 (專利文獻2)特開2002-1 55269號公報 使用如此等之研磨材,可得到且 ^ 胜由、丄 — ^、有某私度之局研磨面 ‘度之被研磨面’但所要求之研磨面精度係逐漸變高。例 =’在如上述之領域的精密研磨中,近年,有時尋求平均 t面粗度㈤為3埃以下、進-步係2埃以下之面精度 =研磨面但在如上述之漿液研磨材或研磨材中,係無法 確保如此高的研磨面精度。 、,因此,為得具有更高之研磨面精度的研磨材,遂研究 平均粒徑更小且粗大粒子之含有率更低的研磨材之開發。 ,如’更微粒之研磨材已知有粒徑為I —以下之所謂超 U粒的氧化;^研磨材。含有氧化鋪等稀土族氧化物的研磨 材,、亦有由鍅與鈽之複合氧化物(Ce-Zr複合氧化物)所 構成的超被粒(例如〇· 〇1 " m左右)之鍅系研磨材(參照 專利文獻3 )。但,即便使用如此等超微粒的研磨材,亦無 法確保充分的研磨面精度。 (專利文獻3)特開平1 0-237425號公報 又’為得到南研磨面精度之技術,係除使用研磨面精 度阿之研磨材以外,尚可舉例:使被研磨體之結晶化玻璃 土板的、、、口日日部結晶粒子之平均粒徑微細化的方法(參照專 利文獻4 ),或’以較玻璃基板之結晶部的結晶粒子徑更小 的小粗彳至磨粒所構成之研磨材進行研磨的方法(參照專利 文獻5) ’或’以矽酸氟表面處理(洗淨)被研磨面之方法, 316680 200535098 或,使用微粒之磨粒且使用漿液濃度較一般更稀釋的漿液 研磨材而進行研磨的方法(參照專利文獻6)等。但,’此 等之技術係任一者均非改善研磨材本身的特性而確保研磨 面精度高之方法。又,為使用此等之技術,必須有更多的 作業,故研磨成本會上昇,研磨作業時間更長。 (專利文獻4)特開2001-1 26236號公報 (專利文獻5 )特許第2 7 3 6 8 6 9號說明書 (專利文獻6 )特開2001-30732號公報 【發明内容】 發明欲解決之課題 本發明係有鑑於如上述之問題點而構成者,課題在於 固::::鈽氧化物等稀土族氧化物作為主成分之氧化物 末而可使用來作為研磨材者,使 可得到研磨面精度高之被研磨面。 (用以角午決課題之手段) 述習明之發明人首先研究有關上 氧化物粒子更微错由使研磨粒子亦即稀土族 易。 ^ 侍到具有更高的研磨面精度係不容 易。因此,著眼於另_ 分 材(稀土族气彳卜仏λ 而開鲞研磨面精度優異之研磨 矢乳化物)。繼而,經 ^ 氧化物之-”卩者眼於稀土族 中氧化鈽與玻璃推彡-儿过 子所S彳寸性,亦即在研磨 (__^^ . 丁匕子反應而破壞玻璃之結合的特性 Q 種研磨作用)。 1 著眼於如此的特性f π知研九之結果,發現於氧化鈽 316680 7 200535098 粒子中產生缺氧,藉提高其缺乏量,可更提昇使用氧化錦 之研磨材的研磨面精度。繼而,進—步研究之結果,發現 為提高缺氧量,使進行作用之元素被氧化錦之構造攝入, 俾提兩氧化飾具有之化學研磨力,甚至可提昇研磨面精 度’終達成本發明。 本發明係以鈽氧化物作為主成分的稀土族氧化物中固 2有絲化物之氧化物固溶體粉末。若使用該氧化物固溶 •胆粉末作為研磨材而研磨玻璃基板等玻璃材,可得到研磨 面:度高的被研磨面。亦即,使用本發明之氧化物固溶體 $末作為研磨村的研磨方法,係適宜作為玻璃基板的研磨 法。使飼兀素固溶於氧化鈽等鈽氧化物所得到之上述氧 =固㈣’係固溶體中所產生之缺氧的缺乏量很高者, 右:乳置两,氧化鈽具有之化學研磨力高’可得到更高的 研“面精度。如此,本發明係關於氧化物固溶體粉末亦即 材其本身之發明’與混合研磨材與溶劑(例如水)而 h 周衣研磨材槳液時藉添加任何的添加劑以提高研磨面精度 之技術,其技術内容根本上相異。 研磨=提ϊ構=:研磨粒子的微粒化可謀求 又旳知π,係在背景技術之處已做說明,但如上 ^ί發Μ使約元素固溶㈣氧化物以提高研磨面精 吏粒子進行微粒化,以提高研磨面精度之技術, 内容亦根本上相異。亦即,本發明之研磨材係盥習 材…即使粒徑相同,亦具有更高的研磨二 又 右依本發明,不須使研磨粒徑微粒化,故粉碎 316680 200535098 或分級之強化不會成為解決課題,不研究有關如此之技術 而可提高研磨面精度。例如。若使用本發明之氧化物固溶 體粉末作為研磨材,藉使用平均粒徑為2"至—左右 者,可得到平均表面粗度(Ra)S3埃(入)或其以下,進 -步係2埃以下之高研磨面精度的被研磨面。又,與研磨 面2之關係非限定平均粒徑,但例如研磨速度一般係粒 T大者〶。因此’在具有比較高之研磨速度者較佳的用途 ’乳化㈣溶體粉末係平均粒徑宜為_以上者,更宜 以上者。繼而’欲極力避免研磨損傷的產生之用途 乳化物固溶體粉末係平均粒徑更宜為^以下者。 本發明之氧化物固溶體粉末宜為鈣元辛之 氧:曰物換算質量之比例為1〇,7、質量二 於氧化鈽等蘇以下者。若上述比例超過上限值, 二 ::稀土族氧化物中約元素完全不被固溶 素以氧化鈣之狀態出現於稀土族氧化 會變高’若如此之氧化鈣存在於研磨材中,::的:此性 或研磨材附著(***產生)之原因。::接ί為研磨損傷 之效果,粆了 >力广 ^ 口月提咼研磨面精度 果係可依鈣氧化物之固溶量所得到 只要飼元素被最低限的量固溶即可(例如,可^親點係 為_質量%以上之固溶量)’但就得到確實效果述比例 f宜為2.0質量%以上。又,為氧化;:之目的’ 、里而该氣化物固溶體之組成進行 、 物固溶體中之各元素以計算氧化物換斤=對於μ 而,在本發明之各稀土族元素之氧化:二出。2 饮w貝!的計算 316680 9 200535098 中’係算出鈣成分等之外的物質不固溶的 換算質量。所謂後述說明所使用之全稀土族氧化 (麵)係使對象物質所含有之全部稀土族 族氧化物而存在時之稀土族氧化物的總質量。稀 在本發明之氧化物固溶體粉末的製造中用以使两元辛 固溶於鈽氧化物所使用的物質(溶質),係宜為硝酸鈣 ㈣或碳酸㈣,即使此等之中,就溶液反應性優之點而 吕,以尤佳。又,所謂稀土族氧化物係例如n 知、敍等稀土族元素的氧化物。 、 使用來作為研磨材之氧化物固溶體粉末係宜以錦氧化 物作為主成分之稀土族氧化物’且固溶有鑭氧化物及 乳化物之氧化物歸體粉末。進行研磨試驗後,鑭元素及^ 或镨兀素被固溶之氧化物固溶體粉末者,較此等未被固溶 之乳化物固溶體粉末,研磨損傷的產生更少,且研磨面精 度優:準備稀土族碳酸鹽(例如碳酸朴培燒此而製造 土知氧化物’右使用綱兀素及/或镨元素被固溶之稀土族 碳酸鹽’可抑制梧燒時之過度的粒子成長,、 傷產生原因之粗大粒子的生成。為得到如此之效果= 物固溶體粉末,氧化質量與氧化錯質量之合計質量佔該 氧化物固溶體的總氧化物換算f量之比例宜為i質量^ 上。但,右該比例超過40質量%,作為氧化物固溶體之安 定性,變低,氧化物固溶體中之元素或镨元素形成氧化 鑭或氧化镨而析出於氧化物固溶體之外的不佳情形易發 生。固此’若著眼於如此之觀點,上述比例宜為4〇質量% ]〇 316680 200535098 以下。 進一步,使用來作為研磨材之氧化物固溶體粉末,宜 為氧化鈽質量佔該氧化物固溶體的總氧化物換算質量之比 例為50質量%以上的氧化物固溶體粉末。換言之,宜為以 氧化鈽為主成分之氧化物固溶體粉末。在由本發明之氧化 物固溶體粉末所成的研磨材中,氧化鈽為最重要的研磨成 分,該氧化鈽的比例為50質量%以下係無法確保安定的研 磨速度。 、"汁九有關挺咼鈣氧化物被固溶於稀土族氧化物中 而成之氧化物固溶體粉末的研磨速度。其結果,在族 氧化物中若絲元素與鉛元素—起固溶,發現可維持研磨 面精度同❹提高研磨速度。因& ’累積進_步研究之姓 果,約與錯之複合氧化物(m〇 CaZr〇〇 &現於研磨财 之研磨材係研磨面精度差,但發現㉟元素及鍅元素之 被固溶於稀土族氧化物中而成的氧化物目溶體粉末係研磨 面精度優。亦即,研磨材用之氧化物固溶體粉末係宜為詞 减物及純化物固溶於”氧化物作為主成分之稀土族 乳:物中之氧化物固溶體粉末。繼而,研究有關固溶之梦 兀素的較適宜含有率。其結果’於氧化錯質量佔氧化物固。 /谷體的總氧化物換算質量之比例宜為〇 ()1質量 若該比例超過上述上限值,研磨粒子之結晶性會降;二 機械性研磨力會減少,故在該比例為下限值以了,益:: 到研磨速度的提高。接著,為得到研磨速度的充分提^ 上述比例更宜為2.2質量%以上。 阿, 316680 11 200535098 士此,本發明之氧化物固溶 故適宜作為研磨材紅右末知研磨面精度優, 於研磨材以外之用v、。 /、他亦具有優異的特性,亦適合 係主成分為軋化气::明之氧化物固溶體粉末 或錯氧化物被固溶者,故:::其:氧化物及/ 性優,更且,且有古”、、 $候性、耐蝕性、安全200535098 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an oxide solid solution, and particularly to a powder of an oxide solid solution containing a rare earth oxide as a main component. [Previous Technology] Rare earth oxides such as hafnium oxide are used in various applications such as abrasives, catalyst carriers, and ultraviolet absorbers. For example, rare earth oxides containing hafnium oxide as a main component are known to be suitable as abrasives, and can be used as glass materials 2 abrasives including optical disks, magnetic disks, 1XD, and HD-shaped glass substrates. Then, in the field of manufacturing electronic devices using glass substrates as described above and using abrasive materials, abrasive materials (rare-earth oxides) are sought for precision polishing. The abrasives used in the above-mentioned fields include, for example, when the slurry of the abrasive is prepared, fluorinated fluoride and sulfuric acid are mixed in the bastnaesite-based abrasive material containing thorium oxide and further mixed. The liquid grinding material obtained from water (refer to patent document υ). The existence of dust in the slurry prevents the sinking of particles in the slurry or the clogging of the grinding dust to prevent the occurrence of grinding damage. Others such as grinding The rare earth carbonate and the dilute / emulsified emulsifier in the main raw material of the material are mixed with chlorinated and pre-fired abrasive materials before the firing step during the manufacture of the abrasive material (see Patent Document 2). : Mixed chlorinated dance before firing can suppress abnormal grain growth during roasting and is easy; mean particle size or particle size distribution during empty roasting can make it easier to produce abrasive materials with small grain size. As a result, even if it does not contain a fluorine component, 3J6680 200535098 can be used to produce an abrasive material that avoids a reduction in the accuracy of the polished surface. (Patent Document 1) Japanese Patent Application Publication No. 6-330025 (Patent Document 2) Japanese Patent Application Publication No. 2002-1 55269 Such abrasive materials Can be obtained and ^ Shengyou, 丄 — ^, there is a certain degree of local polishing surface 'degree of the polished surface', but the required accuracy of the polishing surface is gradually increasing. Example = 'In the precision polishing in the above-mentioned field In recent years, sometimes the average t-plane thickness ㈤ is less than 3 angstroms, and the step accuracy is less than 2 angstroms. Accuracy = grinding surface. However, in the slurry grinding material or grinding material as described above, such high grinding cannot be ensured. Surface accuracy. Therefore, in order to obtain a grinding material with higher grinding surface accuracy, we have studied the development of abrasive materials with a smaller average particle size and a lower content of coarse particles. Oxidation of the so-called ultra-U particles with a particle size of I or less is known. ^ Abrasive materials. Abrasive materials containing rare earth oxides such as oxidized tiles, and also composite oxides of rhenium and rhenium (Ce-Zr composite oxide). ) Made of ultra-fine particles (for example, about 〇1 " m) of stellite-based abrasives (see Patent Document 3). However, even with such ultrafine abrasives, sufficient accuracy of the polished surface cannot be ensured. (Patent Document 3) Japanese Unexamined Patent Publication No. 10-237425 'In order to obtain the precision of the polished surface, in addition to using abrasive materials with a polished surface accuracy, there are also examples: the average particle diameter of the crystal particles of the crystallized glass clay plate of the object to be polished, A method of miniaturization (refer to Patent Document 4), or a method of polishing with a grinding material composed of abrasive grains having a diameter smaller than that of crystal particles of a crystal portion of a glass substrate (refer to Patent Document 5) 'or 'Surface treatment (cleaning) of the surface to be polished with fluorosilicic acid, 316680 200535098 or a method of polishing using abrasive particles with fine particles and using a slurry abrasive material with a more concentrated slurry concentration than in general (see Patent Document 6), etc. However, 'any of these techniques is not a method to improve the characteristics of the abrasive itself and to ensure high accuracy of the abrasive surface. In addition, in order to use these technologies, more work is required, so that the grinding cost is increased, and the grinding operation time is longer. (Patent Document 4) JP 2001-1 26236 (Patent Document 5) Patent No. 2 7 3 6 8 6 9 (Patent Document 6) JP 2001-30732 [Summary of the Invention] Problems to be Solved by the Invention The present invention has been made in view of the problems described above, and has a problem of solidifying :::: rare earth oxides such as rhenium oxide as oxides of main components and using them as abrasives so that a polished surface can be obtained. Polished surface with high accuracy. (Means to solve the problem in the corner of the afternoon) The inventor of Xi Ming first studied the oxide particles more slightly because the abrasive particles, that is, the rare earth group, were easier. ^ It is not easy to wait for higher accuracy of the polished surface. Therefore, we will focus on other materials (milled emulsifiers with rare earth-based gas 彳 彳 λ and excellent accuracy in splitting and polishing). Then, the ^ oxide of the "-" eyes on the rare earth group of osmium oxide and the glass dopant-ergonomic properties, that is, in the grinding (__ ^^. Dingzi reaction to destroy the bond of glass Characteristics Q kind of grinding effect) 1 Focusing on such characteristics f π Zhiyan Jiu results, found that hypoxia 316680 7 200535098 particles produce hypoxia, and by increasing the amount of deficiency, the abrasive material using oxide brocade can be further improved The accuracy of the polished surface. Then, as a result of further research, it was found that in order to increase the amount of oxygen deprivation, the elements that are acting are taken up by the structure of the oxidized brocade. The accuracy is finally achieved. The present invention is an oxide solid solution powder of solid filamentous compounds in rare earth oxides containing rhenium oxide as a main component. If the oxide solid solution and bile powder are used as an abrasive, A glass material such as a glass substrate is polished to obtain a polished surface: a highly polished surface. That is, the polishing method using the oxide solid solution of the present invention as a polishing village is a polishing method suitable for a glass substrate. The above-mentioned oxygen obtained by solid solution of tritium oxide such as thorium oxide = solid thorium 'series solid solution with a high amount of hypoxia deficiency, right: two milk, chemical grinding of thorium oxide The higher the force, the higher the accuracy can be obtained. In this way, the present invention relates to the invention of oxide solid solution powder, that is, the material itself, and the mixing of abrasive materials and solvents (such as water). Technology, its technical content is fundamentally different. Grinding = Lifting structure =: The micronization of the abrasive particles can be sought and known. It has been described in the background art, but as described above, the element solidly dissolves the osmium oxide to improve the fine particles of the abrasive surface. The contents of micronization techniques to improve the accuracy of polished surfaces are fundamentally different. That is, the abrasive material of the present invention is a toiletry material ... even if the particle size is the same, it has a higher abrasive. According to the present invention, it is not necessary to micronize the abrasive particle size, so crushing 316680 200535098 or strengthening by classification will not It is a problem to be solved, and the accuracy of the polished surface can be improved without studying such a technique. E.g. If the oxide solid solution powder of the present invention is used as an abrasive, the average surface roughness (Ra) S3 angstrom (in) or less can be obtained by using an average particle size of 2 to about- Surface to be polished with a high polishing surface accuracy of 2 angstroms or less. The relationship with the polished surface 2 is not limited to the average particle size, but, for example, the polishing rate is generally larger if the particle size T is larger. Therefore, 'the better application is for those having a relatively high grinding rate', the average particle size of the emulsified mash solution powder is preferably one or more, more preferably one. Next, the use of the average particle diameter of the solid solution powder of the emulsion is more preferably ^ or less. The oxide solid solution powder of the present invention is preferably the calcium oxide oxen: the ratio of the mass-equivalent mass is 10,7, and the mass is less than thorium oxide and the like. If the above ratio exceeds the upper limit, two: The rare earth oxides will not be completely dissolved by the solid solution in the state of calcium oxide. The oxidation of the rare earths will become higher. If such calcium oxide is present in the abrasive, : Of: This is the reason for the adhesion of the abrasive material (protrusion). :: The effect of grinding damage is as follows:> Li Guang ^ 口 月 提 咼 The accuracy of the grinding surface can be obtained by the solid solution of calcium oxide, as long as the feed elements are solid solution. For example, the affinity point may be _ mass% or more of the solid solution amount), but the ratio f is preferably 2.0 mass% or more to obtain a definite effect. In addition, for the purpose of oxidation :, the composition of the gaseous solid solution is carried out, and each element in the solid solution is calculated to calculate the oxide exchange weight = for μ, and among the rare earth elements of the present invention, Oxidation: two out. 2 Drink w shellfish! The calculation of 316680 9 200535098 ’is used to calculate the converted mass of a substance other than calcium, which is not solid-soluble. The so-called total rare earth oxide (surface) to be described later is the total mass of the rare earth oxide when all the rare earth oxides contained in the target substance are present. The substance (solute) used to dilute binary solids in the production of the oxide solid solution powder of the present invention to dissolve dioxin is preferably calcium nitrate or europium carbonate, even among these, In terms of the good reactivity of the solution, especially preferred. The rare-earth oxides are oxides of rare-earth elements such as n, y, and y. 2. The oxide solid solution powder used as the abrasive material is an oxide aggregate powder containing rare earth oxides which are mainly composed of bromide oxide and solid solution of lanthanum oxide and emulsion. After the grinding test, the oxide solid solution powders of lanthanum and ^ or lignan are solid-dissolved oxides, compared with these solid solution powders of non-solid-dissolved emulsions, less grinding damage occurs, and the polished surface Excellent accuracy: Prepare rare earth carbonates (such as pak carbonate to produce this earth's oxide, 'Rare earth carbonate with solid solution and / or thorium element' which can be solid-solved 'can suppress excessive particles during burning Growth, the formation of coarse particles that cause injuries. In order to obtain such an effect = the solid solution powder, the total mass of the oxidized mass and the oxidized mass of the oxide should be the proportion of the total oxide converted f of the oxide solid solution. It is above i mass ^. However, when the ratio exceeds 40% by mass, the stability of the oxide solid solution becomes lower, and the element or hafnium element in the oxide solid solution forms lanthanum oxide or hafnium oxide and precipitates out of oxidation. Disadvantages other than solid solutions are likely to occur. In view of this, if the above point is taken into consideration, the above ratio should be 40% by mass] 316680 200535098 or less. Furthermore, oxide solid solutions used as abrasives Powder, preferably It is an oxide solid solution powder whose ratio of the mass of hafnium oxide to the total oxide conversion mass of the oxide solid solution is 50% by mass or more. In other words, it is preferably an oxide solid solution powder containing hafnium oxide as a main component. In the abrasive material made of the oxide solid solution powder of the present invention, hafnium oxide is the most important grinding component, and the ratio of the hafnium oxide to 50% by mass or less cannot ensure a stable grinding speed. Grinding speed of oxide solid solution powder in which the calcium oxide is dissolved in the rare earth group oxide. As a result, if the silk element and the lead element in the group oxide form a solid solution, it is found that the grinding can be maintained. The surface accuracy also improves the polishing speed. Because & 'accumulation progress_ the last name of the research, the complex oxide of about and wrong (m〇CaZr〇〇 & now the grinding material of the grinding material is poor in polishing surface accuracy, but It was found that the rubidium oxide solution powder obtained by solid-dissolving the rhenium element and the lutetium element in the rare-earth oxide is excellent in polishing surface. That is, the oxide solid solution powder for the abrasive material should be a reduced word Purified substance The oxide solid solution powder containing oxides as the main component is the oxide solid solution powder. Next, the content ratio of the dream solution of solid solution was studied. As a result, the oxide solids accounted for the oxide mass. The ratio of the total oxide-converted mass of the cereal grain should be 0 (1) If the ratio exceeds the above upper limit, the crystallinity of the abrasive particles will decrease; the mechanical polishing force will decrease, so the lower limit is at this ratio The value is as follows: It is to increase the grinding speed. Then, in order to obtain a sufficient improvement of the grinding speed, the above ratio is more preferably 2.2% by mass or more. A, 316680 11 200535098 For this reason, the oxide solid solution of the present invention is suitable. As the grinding material red, it is not known that the grinding surface has excellent precision. It is used outside of the grinding material. It also has excellent characteristics. It is also suitable for the main component of rolling gas: Ming oxide oxide solid solution powder or wrong. The oxide is solid solution, so ::: Its: the oxide and / are excellent, and more, and there are ancient ",, weatherability, corrosion resistance, safety
Capac! ty ),具有^麟存脫離能(咖:以咖n Storage 性。因此,本笋明°1不具有可分解有機成分之光觸媒活 車用之觸媒或助觸姐。v』末1先亦適宜作為汽 ^ ’媒又’呂己载於本荦申續真刹r Fi 厂細 媒」中係使用來作為亦包括所,胃促專利跑圍之「觸 所明促進劑的助觸媒之用語。 就本裔明之氧化物固溶體粉末 分之光觸媒活性之點而二於私 八,』刀%有機成 料等所使用之紫外1 作為包含於化粧料或塗 觸姅吱妙外綠'、、吸收劑。又,在觸媒擔體、助觸媒、 、二::卜及收劑之用途使用之粉末的稀土族氧化物固 ::明:::)的使用… 、上°兄月可知’右使用本發明之氧化物固溶體粉末 :例如研磨材’可以高的研磨面精度研磨玻璃基板的玻 祸材’若使用來作為汽車用觸媒擔體等,可提供一種a/f ★(空燃比)之氣體控制特性或氮氧化物的除去性能優異之 觸媒擔體,若使用來作為於化粧料或塗料等所含有的紫外 線吸收劑等各種紫外線吸收劑’可提供具有高的紫外線吸 收能之紫外線吸收劑。 【貫施方式】 316680 12 200535098 (用以實施發明之最佳形態) 以下,一面參照圖及表,一面說明有關本發明之氧化 物固〉谷體粉末的適宜的實施形態。 1貫施形態:在本實施形態中,準備碳酸飾、碳酸鑭、 碳酸镨及碳酸鈣,將此等分別溶解於硝酸水溶液中,藉過 濾、除去異物後,加入純水,以氧化物質量換算調製20Og/L (克/升)之硝酸鈽水溶液、硝酸鑭水溶液、硝酸镨水溶液 I 及硝酸鈣水溶液。 首先,混合硝酸鈽水溶液3〇〇ml (毫升)、硝酸 I闌水溶液15OnU、硝酸镨水溶液35m卜硝酸飼水溶液15m 1, 進步加入純水而得到3升之混合液(步驟1,參照第1 圖)此叱合液所含有之各稀土族元素及鈣之氧化物換算質 量的比例為6 0 : 3 η · 7 · Q广r η . τ ^ j 勹叫川· 7 · 3 (二Ce〇2 · La2〇3 : PreO】】:CaO)。 又,準備1. 2倍當量的碳酸氫銨水溶液2升(84g/升 > 繼 而’一面授拌先前得到之混合液的全量,—面滴入於呈 # 350rPm之強授拌狀態的碳酸氫銨水溶液中而得到含碳酸 =共广殿粒子(步驟2)。滴下時之饋入速度為5〇ml/分。 其二人’使含有共沈澱粒子縣 跡+ 卞心心,蜀液在室溫下熟成2小時(步 驟3),使用純水稀釋熟成後之縣 經夕q 欠心心濁液至20升。靜置所稀 釋之心濁液3小時而使丘沈资 進行傾叔““ 子沈澱(步驟4)。靜置後, 進仃傾析至所沈澱之共沈 5 ),苴诒说1 丁的粗積達4升以下(步驟 洗淨中,進行洗淨至懸濁液中(步驟6)。在該 下,得到含共沈殿粒子之 -欠料濃度為2〇PPm以 “ 夜。洗淨後,過濾含共沈澱 316680 13 200535098 粒子=濁液而得到共沈激粒子的遽餅(cake)(步驟7)。 便’以熱風乾燥機(熱風溫度12〇t、乾 ::)乾燥所得到之濾餅(步驟8),敲碎 之; (步驟9 ),以雷^♦说古卜上J <專乙/木口口 鍛燒時間3小時)『牛J J「進仃锻燒(锻燒溫度3〇(rC、 子)(牛π n/ v 0)、破碎鍛燒品(所謂去碳酸粒 (Ce二乍VV小時)培燒(步驟12)、得到在以氧化鈽 '容的气化Γπ 之稀土族氧化物中氧化临0)被固 ==溶體(稀土族元素-Ca複合氧化物)。繼而, 溶"::溶體(步驟13)而得到研磨材(氧化物固 此稀 ㈣ 又’ 作為主成八矢# 中包含以稀土族氧化物 =:之:化物固溶體,而使用所謂該「稀土族氧化 研二 ’對於在各實施例或比較例中所得到之 :磨子,而使用所謂「稀土族氧化物」之用語 氧化物二無乳化物」中包含在稀土族氧化物以外的 乳化物固溶於稀土族氧化物之氧化物固溶體。 此等之實施例及比較例,係 量合狀態中之各稀土族元素的氧化物換算重 =例不同。在各實施例及比較例中之混合比例,係如 之、說:此以外之點係與實施们相同,故省略其等 在1本比較例中,係以習知之製造方法製造研磨 。百先,準備碳酸鈽、碳酸鑭、碳酸鳍而得到此等之混 316680 14 200535098 合物(200g)。該混合物邮人+ ^ 物所έ有之稀土族元素的氧化物換嘗 重夏之比例為 62:3l:7(=Ce〇2:U2〇3:Pr6〇11)。繼而 1 準備2個塑膠容器(容ςηη ιλ + # 、k而, 、 里均為500ml ),在各塑膠容哭由 之此合物所秤取的100g混合物、粒押 〇· 8mm的氧化鍅粒子]8nn ^ 器GW Shaker)進行3=純*使用漆料振盪 小日寸之 >絲式混合粉碎。其後, 所得到之混合物使用3G篩目(網眼·"} < 了粒子後,過濾’而得到稀土族碳酸鹽的濾餅。繼而, ㈣風乾所得狀結塊(熱風溫度12代、乾^ 日守間8小時),敲碎乾燥品,以電氣爐培燒所敲碎 (培燒溫度9啊、料㈣3小時)、敲碎料品而得^ 研磨材。所得到之研磨材的平均粒#為38_。 以 至 ' .此等之比較例,係與實施例3在混合物狀 中之各稀土族元素的氧化物換算重量之比例不同。 比較例中之該比例,係如表丨所示般。 .本比較例中係準備已知之高純度膠體氧化石夕作 為玻璃基板之精密研磨用。膠體氧切之平均粒徑為〇 06 // m 〇 錢實施例丨至5的研磨 材及比較例u的研磨材,使用x線繞射裝置咖8 :Capac! Ty), has the ability to escape from the ground (ca: storage capacity. Therefore, the bamboo shoots ° 1 does not have photocatalysts that can decompose organic ingredients, or catalysts for car use. V 』End 1 It is also suitable to be used as a steam engine ^ 'Medium again' Lu Ji Zai in the fine media of this company's continued true brake r Fi factory "is used as a" catalyst of the catalyst that touches the accelerator of the stomach " Terms. In terms of the photocatalytic activity of the oxide solid solution powder of native origin, it is better than the private one. "Ultraviolet 1 used in organic materials, such as knives, is included as a cosmetic or coated with squeegee." 、, absorbent. In addition, the use of powdered rare earth oxide solids :: Ming :: :) used in the catalyst carrier, catalyst, ...: It can be seen that 'the right use of the oxide solid solution powder of the present invention: for example, a grinding material', a glass material which can grind a glass substrate with high grinding surface accuracy ', if used as a catalyst carrier for automobiles, etc., a / f ★ (air-fuel ratio) catalyst carrier with excellent gas control characteristics or nitrogen oxide removal performance, if Various UV absorbers such as UV absorbers contained in cosmetics or coatings can provide UV absorbers with high UV absorption energy. [Application Method] 316680 12 200535098 (The best form for implementing the invention ) Hereinafter, a suitable embodiment of the oxide solids> cereal powder according to the present invention will be described with reference to the drawings and tables. 1 Implementation mode: In this embodiment, carbonic acid decoration, lanthanum carbonate, thorium carbonate, and carbonic acid are prepared. Calcium was dissolved in an aqueous solution of nitric acid. After filtering and removing foreign matters, pure water was added to prepare an osmium nitrate aqueous solution, a lanthanum nitrate aqueous solution, and an osmium nitrate aqueous solution in an amount of 20 Og / L (g / l) in terms of oxide mass conversion. And calcium nitrate aqueous solution. First, 300 ml (ml) of ytterbium nitrate aqueous solution, 15 OnU of nitric acid nitrate solution, 35 m of ytterbium nitrate aqueous solution, and 15 m of nitric acid feed solution were added, and 3 liters of mixed solution was gradually added (step 1). (Refer to Figure 1.) The ratio of the converted mass of each rare earth element and calcium oxide contained in this mixed solution is 6 0: 3 η · 7 · Q 广 r η τ ^ j 勹 叫 川 · 7 · 3 (二 Ce〇2 · La2〇3: PreO]: CaO)。 Also, prepare 1.2 liters of equivalent ammonium bicarbonate aqueous solution 2 liters (84g / liter >) 'While mixing the entire amount of the previously obtained mixed solution, dripping it into an aqueous ammonium bicarbonate solution with a strong mixing state of # 350rPm to obtain carbonic acid = Gongguangdian particles (step 2). Feeding when dropping The speed is 50ml / min. The two of them "make the prefecture containing co-precipitated particles + 卞 心心", and the Shu liquid is matured at room temperature for 2 hours (step 3), and the matured prefecture Jingxi is diluted with pure water. Turbidity to 20 liters. The dilute heart turbid solution was allowed to stand for 3 hours, and then Qiu Shenzi was allowed to pour out the undeposited particles (step 4). After standing, it was decanted to a total precipitation of 5), and the coarse product of 1 d was less than 4 liters (in the step of washing, it was washed into the suspension (step 6). Next, the concentration of co-sinking particles with an underfeed concentration of 20 PPm was obtained. After washing, the co-precipitated 316680 13 200535098 particles were filtered to obtain a cake of co-precipitated particles (step 7). ). Then 'dry the obtained filter cake (step 8) with a hot air dryer (hot air temperature 120t, dry :), and crush it; (step 9), say Lei ^ ♦ Gubu J < Special B / Kokuguchi calcination time 3 hours) "Bull JJ" Into the calcination (calcination temperature 30 (rC, child) (bovine π n / v 0), broken calcined products (the so-called decarbonation (Ce The second time, VV), the calcination (step 12), to obtain the oxidation of the rare earth oxide in the vaporized Γπ with the content of yttrium oxide, the solid oxide = solid solution (rare earth element-Ca composite oxide). Then, dissolve ": solution (step 13) to obtain the abrasive material (the oxide is solid, and the rare earth oxide is also used as the main component of the eight vector #. Contains the rare earth oxide =: of: a solid solution, and use Called the "Earth rare earth oxide research second" is obtained in each example or comparative example: mill, and the term "rare earth oxide" is used. Oxide di-emulsion-free emulsion is included in addition to the rare earth oxide. The solid solution is an oxide solid solution of a rare earth oxide. In these examples and comparative examples, the oxide conversion weight of each rare earth element in the combined state is different from the example. The examples and comparative examples are different. The mixing ratio in the system is the same as that described above: the other points are the same as those of the implementers, so they are omitted. In this comparative example, grinding is performed by a conventional manufacturing method. Baixian prepared rhenium carbonate and lanthanum carbonate And carbonic acid fins to obtain such a mixture 316680 14 200535098 compound (200g). The ratio of the oxide of the rare earth element in the mixture + ^ thing in exchange for heavy summer is 62: 3l: 7 (= Ce 〇2: U2〇3: Pr6〇11). Then 1 prepare 2 plastic containers (capacity ηη ιλ + #, k, and, both are 500ml), weighed in each plastic container by this composition 100g mixture, granules of 0.8mm ytterbium oxide particles (8nn ^ Shaker) 3 = Pure * Use paint to oscillate small-day-of-days > wire-type mixing and pulverization. After that, the obtained mixture is filtered with 3G mesh (mesh · "} < after filtering the particles to obtain rare earth carbonic acid Salt cake. Next, ㈣ air-dried the cake (hot air temperature 12 generations, dry ^ 8 hours between days), crush the dried product, and crush it in an electric furnace (cooking temperature 9 ah, charge 3) Hours), crushed materials to obtain ^ abrasive material. The average particle # of the obtained abrasive material is 38 mm. As for the comparative examples, the ratios of the oxide-equivalent weights of the respective rare-earth elements in the mixture state to those in Example 3 are different. The ratio in the comparative example is as shown in Table 丨. In this comparative example, a known high-purity colloidal oxidized stone is prepared for precision polishing of a glass substrate. The average particle size of the colloid oxygen cut is 〇 06 // m 〇 The grinding material of Examples 丨 5 and the grinding material of Comparative Example u, using the X-ray diffraction device coffee 8:
Maxsc跳e (股)製)而進行XR])測定。在本測定中係使 用銅㈤)μ,照射Cu‘Ka線來測定Cum燒射 X、·泉強度。接著’其他之測定條件係Maxsc jumps to e (share) system and performs XR]) measurement. In this measurement, copper ㈤) μ was used, and Cu'Ka rays were irradiated to measure the Cum firing X and the spring intensity. Next ’other measurement conditions are
150mA、測定苑圍 26=5。至训。π 4,A ^ " "L ^ Z ^ °主90 、取樣幅寬0· 02。、掃描 316680 200535098 速度4. (Γ /分。測定結果(XRD圖譜)係如第2圖所示般。 又,在圖2中,為容易讀取圖譜,有關實施例2之研摩"材 以外的研磨材之圖譜係使基線(base level)朝上移位而 現於圖上。 、 如第2圖所示般,全部之研磨材的XRD圖譜係於3。150mA, 26 = 5. Extreme training. π 4, A ^ " L ^ Z ^ ° Mainly 90, sampling width 0. 02. Scanning 316680 200535098 Speed 4. (Γ / min. The measurement result (XRD pattern) is as shown in Figure 2. In addition, in Figure 2, for easy reading of the pattern, related to the study of Example 2 The spectrum of the abrasive material is shifted upwards from the base level and appears on the map. As shown in Figure 2, the XRD spectrum of all the abrasive materials is 3.
(=2 0 )附近、及於32· 5。附近出現譜峰。此等之譜峰係 表示立方晶氧化鈽的存在。繼而,在各實施例之研磨材的 XRD圖譜(2θ=20。至40。的測定範圍)中未出現上述譜 峰以外之譜峰。另外,在比較例iiXRD圖譜係於37Y 附近出現在實施例中未存在的譜峰,在比較例2中xrd圖 譜係於32.3。附近及於37·5。附近出現在實施例中未存 在的譜峰。此等之譜峰係表示氧化鈣(CaO)存在之譜峰。 如此之XRD測定的結果可知,在各實施例丨至5的研 磨材中’係原料中之躬元素全部固溶(完全固溶)於稀土 族氧化物中,但在顯示氧化鈣存在之譜峰出現的比較例 卜2的研磨材中,係鈣元素完全不固溶(為不完全固溶), :以氧化鈣出現於研磨粒子之稀土族氧化物粒子外側的狀 恶存在(翏照表1之CaO有無之欄)。 ·對於各實施例及比較例所得到的研磨材,使用 :斯卡型研磨機進行研磨試驗。研磨試驗方法係使用貼有 κ胺基甲i酯製之研磨墊的直徑1 8⑽瓜常盤而同時研磨3 片直牷30mm之圓板形狀的玻璃材(βΚ —7製、被研磨材)。 百先,使用各實施例及比較例所得到的研磨材而調製研磨 k液0 · 1升’將所調製之研磨材漿液以3升/分之比例循 316680 16 200535098 環供給而進行研磨試驗。研磨時之研磨塾的旋轉數為 33rPm、擺動旋轉數為3〇rpm、擺動幅為⑽画。又,研磨麼 力為19. 6kPa ( 200g/cm2),研磨時間為3〇分。 又,研磨試驗中之研磨材漿液的調製如以下般。在久 實施例及比較例U中,係在室溫下混合揽拌粉末狀之研 磨材與純水,而調製研磨材漿液全體占有之研磨材的比例 為|〇質量%的研磨材襞液〇1升。繼而,在比較例3至7 ,中备在至皿下5攪拌粉末狀之研磨材、氯化鈣粉末與 水’而調製於漿液全體占有之研磨材的比例為ι〇質量%的 研^才衆液0.1升。在比較例3至7中之氣化絲末之混 合量’係研磨材聚液中之碎元素的質量比例,表示於表! 之值的量。該混合量係以如下基準所訂定的量,即該基準 係,實施例1至5的研磨材衆液中㈣元素的質量比例與 幸乂例3至7之研磨材毁液的懸濁液中之妈離子(+) 的質量比例形成相同程度。在比較例8中係準備 氣化石夕製液25g’將此與純水75ml在室溫下混合攪 。、、周製於研磨材漿液全體占有之研磨材的比例為Μ質量 %的研磨材漿液〇 · 1升。 、 研磨終了後,以純水洗淨玻璃材 ^研磨面而以無塵狀態乾燥後,㈣研磨對象物之減少 :又(㈣’使用由該厚度與研磨時間所算出之「 =之減少厚度(# m/分)」而評估研磨速度。又 2顯微鏡Ut⑽lciorcemicrosc〇pe;朗而測定平 :、面粗度(Ra)’使用此而評估被研磨面之研磨面精度。 316680 17 200535098 各實施例及比較例之研磨材的研磨速度及研磨面精度係如 表1所示般。 [表1 ] 鈽系研磨材 組成 TRE0 (wt°/o) 研磨特性(= 2 0), and at 32.5. Spectral peaks appear nearby. These spectral peaks indicate the presence of cubic osmium oxide. Then, no X-ray diffraction pattern (measurement range of 2θ = 20. To 40.) of the abrasive material of each example showed no spectral peak other than the above-mentioned spectral peak. In addition, in the comparative example iiXRD spectrum system, a peak that does not exist in the examples appeared near 37Y, and in Comparative Example 2, the xrd spectrum system was 32.3. Nearby and at 37.5. Nearby, peaks which did not exist in the examples appeared. These spectral peaks represent the spectral peaks in which calcium oxide (CaO) is present. As a result of the XRD measurement, it can be seen that all the elements in the 'series raw materials in the abrasive materials of Examples 1 to 5 were solid-dissolved (completely dissolved) in the rare-earth oxide, but the peaks showing the presence of calcium oxide In the abrasive material of Comparative Example 2 that appeared, the calcium element was completely insoluble (being incompletely soluble), and the presence of calcium oxide appeared outside the rare earth oxide particles of the abrasive particles (see Table 1) (CaO has no column). · The abrasive materials obtained in the examples and comparative examples were subjected to a polishing test using a ska type grinder. The polishing test method is to simultaneously grind 3 pieces of circular plate-shaped glass material (made of βK-7, a material to be polished) having a diameter of 18 mm, and a polishing pad made of κ aminomethyl ester. Baixian used the grinding materials obtained in the examples and comparative examples to prepare and polish k liquid 0 · 1 liter '. The prepared grinding material slurry was fed at a rate of 3 liters per minute in a ring of 316680 16 200535098 to perform a grinding test. The number of rotations of the grindstone during grinding was 33 rPm, the number of swing rotations was 30 rpm, and the swing width was black. The polishing force was 19.6 kPa (200 g / cm2), and the polishing time was 30 minutes. The preparation of the abrasive slurry in the polishing test was as follows. In the long examples and comparative examples U, powdered abrasives and pure water were mixed at room temperature, and the ratio of the abrasives occupied by the entire abrasive slurry was adjusted to 0% by mass of the abrasive slurry. 1 littre. Next, in Comparative Examples 3 to 7, Zhong prepared under the plate 5 stirred the powdery abrasive material, calcium chloride powder, and water, and the ratio of the abrasive material prepared to the entire slurry was 5% by mass. Mass liquid 0.1 liter. The mixing amount of the vaporized filaments in Comparative Examples 3 to 7 'is the mass ratio of the broken elements in the abrasive liquid, shown in the table! The amount of value. The mixing amount is determined based on the following standard, that is, the reference system, the mass ratio of the thorium element in the abrasive liquids of Examples 1 to 5 and the suspension of the abrasive liquids of Examples 3 to 7 The mass ratio of the mother ion (+) is formed to the same degree. In Comparative Example 8, 25 g of a gasified syrup solution was prepared and mixed with 75 ml of pure water at room temperature. The ratio of the grinding material occupied by the whole grinding material slurry to the grinding material slurry is 0.001% by mass. After the grinding is completed, the glass material is washed with pure water and the polished surface is dried. After the grinding is done in a dust-free state, the reduction of the grinding object is reduced: again (㈣ 'uses the reduction thickness calculated from the thickness and the grinding time "= # m / 分) "to evaluate the polishing speed. Another microscope Ut⑽lciorce microscoppe; Lange measurement flat, surface roughness (Ra) 'is used to evaluate the polishing surface accuracy of the surface to be polished. 316680 17 200535098 Examples and The polishing rate and polishing surface accuracy of the polishing material of the comparative example are shown in Table 1. [Table 1] Composition of the sacrificial polishing material TRE0 (wt ° / o) Polishing characteristics
嶔4) 研磨材 漿液中 之 Ca2, 的比例 (重量« ※1 )研磨材為膠體氧化矽 TRE0中之各稀土族氧化物 的含有率(重量%)嵚 4) Proportion of Ca2 in slurry (weight «※ 1) Content of each rare earth oxide in colloidal silica TRE0 (wt%)
雌=)2對於原料巾之稀土族元素及^元素之總氧化物換 #开貝1的Ca元素質量之比例。 =3)「「無」係表示未被XRD測定檢測出,「有」係表示檢測 Ca成分^原料中未添加以,而於研磨材粒子中Ca〇等 Ϊ I *^Γ,'f I" ^ ^ 6 ^ ^ ^ ^ ^ ( Ca-) 如 」係表示於漿液中未添加鈣離子。 ^ °表1所示般,實施例1至5之研磨材户征-主 :稀土族氧化物中完全者 素固溶 檢測出。& ^ 果,無虱化鈣之 、而’貫施例1至5之研磨材中係原料中之飼元 316680 18 200535098 素的比例愈多,研磨面精度愈優。又,各實施例之研磨材 係與比較例8之研磨材(膠體氧化石夕)比較,研磨粒子徑 係明顯大徑,但研磨面精度係相同或較其更優,研磨速度 亦相同或較其更高。 另外’比較例1,2之研磨材係㉝元素之固溶不完全 者,XRD測定之結果,有氧㈣之檢測出。繼而,比較例 1,2之研磨材係研磨球声盘途^ 疋度舁貝施例4, 5或比較例8(膠體氧 切)之研磨材相同,但不只原料中之_元素的比例高於 貫施例,研磨損傷常產生且研磨面精度差。 此結果可知,當製造㈣元素固溶於稀土族氧化物之 錦ί研磨材時,研磨材係宜完全固溶詞元素,且研磨粒子 乳化物固溶體粒子)之外不出現氧化_者’㉟元素質量 物,之總氧化物換算質量之比例宜為2. 〇質量%至、 Μ· 7質量%(更宜為7. 15質量%以下)。 又’在研磨材中檢測出氧化巧之比較例卜2的研磨材 二原料中之鈣元素的比率例高,研磨損傷愈多,有研磨 口 4度差之傾向。此傾向係與專利文獻2之表2所示的穿』 叩研磨試驗結果(參照專利文獻2之表2的實施例3至;: 比較例3的傷痕值)相同的傾向。此結果可知,使用專 〇獻2之實施例3至5或比較例3之研磨材的製造方法、 =所謂只使碳酸稀土族等(碳酸稀土及/或氧化烯土)盘 、=屬鹽及/或驗土族金屬鹽混合而培燒之研磨材製造方 二係無法製造-種於稀土族氧化物中鹼土族元素被完全 4溶之研磨粒子,而同於與本發明實施例之比較所使用的 316680 19 200535098 比歧例卜2之研磨材,研磨材巾 1 ^ , τ θ 現鹼土族氧化物。 ’如表1所示,使鈣離子(c彳 液的懸濁液中之比較例3至76广)存在於研磨材滎 ! ^ 5 勺研磨材,係相較於實施例 5 :研磨材而研磨面精度明顯變差。此結果可知,為 “ Μ面精度使蘭成分時 ^ 不以鈣離子之灿&人士 竹给材水液的%濁液中 、择 悲含有,而如實施例1至5般,宜使用在 以氧化鈽作為主成分的稀土族氧化 全固溶)之氧化物固姊 +乳化妈被固洛(完 1化物固洛體粉末作為研磨材。又,在研磨材繫 &所使用之碳㈣精鑛等研磨材原料或工業用水之中係 ::土族金屬鹽等狀態含有物,有時源自此等之㈣ 子冒不可避免地殘留於研磨材聚液的懸濁液中,但鈣離子 之殘留恐會使研磨面精度降低,宜極力避免。 :研究研磨面精度、 與研磨材之總氧化物換算質量占有㈣元素之 關係。 • 如示於帛3圖中,實施例5(於稀土族氧化物中妈 兀素固溶之研磨材)之時,鈣元素之比例超過0質量%,不 足2質量%的範圍(尤其〇. 5質量%以上之範圍)中,鈣元 素之比例愈高,研磨面精度愈提高。鈣元素之比例為2質 量%以上的範圍’係可得到安定而優之研磨面精度。此結果 可知,就提供具有優異之研磨面精度的研磨材而言,宜含 有鈣元素。繼而,為使高研磨面精度安定而確保,鈣元素 之比例宜為0. 5質量%以上,更宜為2質量%以上。但,若 考量先前說明之研磨傷痕等,其比例宜為Ι〇·7質量%以 316680 200535098 下,更宜為7· 15質量%以下。 另外,在比較例3至7的研磨材(縣 在之研磨材漿液)中,其;^ 巾飼離子存 -主 面精度係無關於所含有之钮 兀不之質量比例而相同。亦即, ·. 液中僅以_子等狀態添加約成分製時,在溶 度等研磨特性不會提高。 力磨面精度或研磨速 差:其次說明有關另一每竑形处丄 係關於氧化鈽之含有率高之所:二::施形態 月回口口貝之鈽糸研磨材。 研磨材製造時,·混合液之際進行混合 石、’酸鈽水溶液、㈣鑭水溶液、硝酸镨水溶液、硝酸約 =…昆合比例與第1實施形態相異。在各實施例之混 口液中的各稀土族元素簡之氧化物換算質量的比例如表 所不般。此以外之條件係與第丨實施形態之實施例丨相 同。 本比較例係與上述實施例6至9相異,原 •料中未添加飼成分。又,在比較例9至12巾,使研磨材之 稀土族元素之氧化物換算質量的比例如對應於上述實施例 6至9中之該質量比例而設定。此以外之條件係與實施例6 至9相同。 對於實施例6至9的研磨材進行上述xrd測定而評估 〇之有無’對於實施例6至9及比較例9至1 2的研磨材 、亍上述研磨6式驗而評估研磨面精度及研磨速度。結果如 、 所不般’又,在研磨試驗中之研磨材漿液的調製方法 ir、任一貫施例及比較例所得到的研磨材之情形均與第1實 316680 200535098 施形態之各實施例相同。[表2] 實施例6 XI) 原料 中之 Ca的 質量 (重 量〇/〇 5. 003 ——-_材 - 組成 -- 平均 粒徑 ΰδΟ (μ m) 9 9 A TRE 0 (重 量°/〇 92.98 ※2) CaO 之 有 無 益 TRE0 化物έ 中之各稀土匆 1勺含有率(曹^ ^氧 f °/ο) Ce〇2 97.00 LazO 3 3. 00 Ptg〇 11 0.00 Nd2〇 3 0. 00 貫施例7 實施例8 π η π 92.99 92. 98 96.98 94.01 TooH 2.98 3. 00 2. 99 0.02 0.02 無 益 ^ · L· 2. 98 ? A A 貫施例9 比較例9 92.97 96. 98 100 97.01 0 2. 99 〇. 00 0 π no 無 厶· 4分 3. 02 比較例10 比較例11 比較例12 V/ · U U 96.99 96.98 94.97 96. 99 94.02 100 0. 00 3.〇Γ^ 0 2. 99 υ. υζ 0.02 一 3. 27 4. 76 2.96 1 0.02 0 — 3. 58 沄3) 研磨材 漿液中 之 Ca2: 的比例 (重量%) 成1、 士口 #丄士人広、ϊ,、ι丄、_ 性 特 磨 研Female =) 2 For the ratio of the total oxides of the rare earth elements and ^ elements in the raw material towel # Cabe1. = 3) "None" means that it has not been detected by XRD measurement, "Yes" means that the Ca component has been detected ^ is not added to the raw material, and Ca〇 等 Ϊ I * ^ Γ in the abrasive particles, 'f I " ^ ^ 6 ^ ^ ^ ^ ^ (Ca-) "" means that no calcium ion was added to the slurry. ^ As shown in Table 1, the abrasive materials of Examples 1 to 5-Main: Complete solution of rare earth oxides was detected. & ^ As a result, there is no calcification of lice, and the higher the ratio of feed element 316680 18 200535098 in the raw materials of the abrasive materials of Examples 1 to 5, the better the accuracy of the polished surface. In addition, compared with the abrasive material (colloidal oxidized stone) of Comparative Example 8, the abrasive particle diameter of each example is significantly larger, but the accuracy of the abrasive surface is the same or better, and the polishing speed is the same or better. It's higher. In addition, in the case where the solid solution of the rubidium element of the abrasive materials of Comparative Examples 1 and 2 was incomplete, the result of XRD measurement was the detection of aerobic radon. Then, the abrasive materials of Comparative Examples 1 and 2 are grinding ball sound disks. 疋 Degrees are the same as those of Example 4, 5 or Comparative Example 8 (colloid oxygen cutting), but not only the proportion of _ elements in the raw materials is high. In the examples, abrasive damage often occurs and the accuracy of the abrasive surface is poor. From this result, it can be known that, when manufacturing the abrasive material of rhenium element which is dissolved in rare earth oxides, the abrasive material should be completely solid-soluble, and no oxidation occurs outside the abrasive particle emulsion solid solution particles) The mass ratio of the element element to the total oxide is preferably from 2.0% by mass to M · 7% by mass (more preferably, 7.15% by mass or less). In Comparative Example 2 where the oxide was detected in the abrasive material, the abrasive material of Comparative Example 2 had a higher ratio of calcium element in the second raw material, and the more the abrasive damage was, the worse the polishing mouth tended to be 4 degrees. This tendency is the same tendency as the wear test results shown in Table 2 of Patent Document 2 (refer to Examples 3 to in Table 2 of Patent Document 2; the flaw value of Comparative Example 3). From this result, it can be seen that the manufacturing methods of the abrasives of Examples 3 to 5 or Comparative Example 3 using the special method 2 are: so-called only rare earth carbonates (rare carbonate and / or oxyalkylene earth) disks; / Or grinding materials produced by mixing the earth metal salts and firing them cannot be produced-the kind of abrasive particles in which the alkaline earth elements in the rare earth oxides are completely dissolved, which are the same as those used in comparison with the examples of the present invention The 316680 19 200535098 ratio of the abrasive material of Example 2 and the abrasive material towel 1 ^, τ θ are alkaline earth oxides. 'As shown in Table 1, calcium ions (Comparative Examples 3 to 76 in the suspension of the C solution) were present in the abrasive material 荥! 5 spoons of abrasive material, compared with Example 5: Abrasive material The accuracy of the polished surface is significantly deteriorated. From this result, it can be seen that when the ML surface accuracy is such that the blue component is not included in the% turbid liquid of the bamboo water solution of the calcium ions, it is preferably contained in the turbid solution, but as in Examples 1 to 5, it should be used in The rare earth oxidized total solid solution with osmium oxide as the main component is an oxide solid solution + emulsified morocola (finished 1 bolus solid body powder as the abrasive. Also, the carbon material used in the abrasive material & Raw materials such as concentrates or industrial water: :: Turk metal salts and other state-contained substances, sometimes derived from these maggots inevitably remain in the suspension of the abrasive liquid, but calcium ions Residuals may reduce the accuracy of the polished surface and should be avoided as much as possible.: Investigate the relationship between the accuracy of the polished surface and the total oxide conversion mass occupied by the rubidium element. • As shown in Figure 3, Example 5 (in rare earth In the case where the matrix oxide is a solid-solution grinding material), the proportion of calcium element exceeds 0% by mass and less than 2% by mass (especially the range of 0.5% by mass or more), the higher the proportion of calcium element , The more accurate the polishing surface. The proportion of calcium element is 2 The range of "% by weight or more" means that stable and excellent polishing surface accuracy can be obtained. From this result, it is understood that it is desirable to include a calcium element in order to provide a polishing material having excellent polishing surface accuracy. Then, in order to stabilize the high polishing surface accuracy, Ensure that the proportion of calcium element is preferably 0.5 mass% or more, more preferably 2 mass% or more. However, if the grinding scars and the like described above are taken into consideration, the proportion should be 100.7 mass% to 316680 200535098 or more. It should preferably be 7.15% by mass or less. In addition, in the abrasives (abrasive slurry of the county) in Comparative Examples 3 to 7, its: ^ Feed ion storage-main surface accuracy is not related to the contained buttons The mass ratio is the same. That is, ·. When only about ingredients are added in the liquid state, the grinding characteristics such as solubility will not be improved. The precision of the grinding surface or the grinding speed difference: Secondly, it explains that another The 竑 -shaped part is the place where the content ratio of osmium oxide is high: 2 :: Shi Fengyue grinding material for oyster shells. When grinding materials are manufactured, mixed stones, 'acid solution, Thorium lanthanum aqueous solution, thorium nitrate aqueous solution Nitric acid is approximately equal to ... The ratio of kunhe is different from that of the first embodiment. The ratio of the oxide-converted mass of each rare earth element in the mixed solution of each example is as shown in the table. Other conditions are the same as those of the first embodiment.丨 The examples of the implementation form are the same. This comparative example is different from the above-mentioned examples 6 to 9, and no feed ingredients are added to the raw materials. In addition, in Comparative Examples 9 to 12, the rare earth elements of the abrasive material are changed. The ratio of oxide-based mass is set, for example, in accordance with the mass ratio in Examples 6 to 9. The other conditions are the same as those in Examples 6 to 9. The abrasive materials of Examples 6 to 9 are subjected to the above-mentioned xrd measurement and Evaluation of “Presence of 0” For the polishing materials of Examples 6 to 9 and Comparative Examples 9 to 12, the polishing surface accuracy and polishing rate were evaluated according to the above-mentioned polishing 6 tests. The results are different, and the method of preparing the grinding material slurry in the grinding test, the grinding material obtained in any of the conventional examples and the comparative examples are the same as those in the first embodiment of the first embodiment 316680 200535098. . [Table 2] Example 6 XI) The mass of Ca in the raw material (weight 〇 / 〇5. 003 ---_ material-composition-average particle diameter ΰδO (μm) 9 9 A TRE 0 (weight ° / 〇 92.98 ※ 2) The content of CaO with or without TRE0 is 1 scoop of each rare earth (Ca ^ ^ oxygen f ° / ο) Ce〇2 97.00 LazO 3 3. 00 Ptg〇11 0.00 Nd2〇3 0.00 Example 7 Example 8 π η π 92.99 92. 98 96.98 94.01 TooH 2.98 3. 00 2. 99 0.02 0.02 No benefit ^ · L · 2. 98? AA Example 9 Comparative Example 9 92.97 96. 98 100 97.01 0 2 .99 〇. 0 0 0 π no None. 4 minutes 3. 02 Comparative Example 10 Comparative Example 11 Comparative Example 12 V / · UU 96.99 96.98 94.97 96. 99 94.02 100 0. 00 3.〇Γ ^ 0 2. 99 υ υζ 0.02-3. 27 4. 76 2.96 1 0.02 0 — 3. 58 沄 3) The proportion of Ca2: in the abrasive slurry (% by weight) becomes 1. 士 口 # 丄 士人 広, ϊ, ι 丄, _ Sex special grinding research
磨精Ra^) 研面度C 磨度::一分 研速 ¢111/ 76 ο ο· 4 3 2· 5 6 4· 74 0781 1·- 8 6 ο 々、外竹丫(稀土族元素及Ca元素之總氧化物換 算質量的Ca元素質量之比例。 ※2 )「無:係表示未被χ R D測定檢測出,「有」係表示檢測 出 」(了'方、原料中未添加Ca ’而於研磨材粒子中Ca〇等 之Ca成分未存在。 ※㈦研磨材滎液之總質量占有的已添加之詞離子(c 之質罝比例,「-」係表示於漿液中未添加飼離子。 從表2所示之結果可知, ,,^ IV . /L 即使在所明咼品質之研磨材 中,由方;乂乳化鈽作為主成分的稀土族氧 溶(完全固溶)之氧化物固 丫礼化约U π於第^谷组粉末所成之錦系研磨材,係 Μ弟的研磨材,與氧㈣ 比較,具有優異之研磨面精度。 之研泣材 第3錢:其次進-步說明有關另-實施形態。本杏 施形態係於稀土族氧化物中不僅〜v只 吏乳化舞,亦使氧化錯固 3]6680 22 200535098 /谷之氧化物固溶體所成之鈽系研磨材。Grinding Ra ^) Grinding surface C Grinding degree: One-point grinding speed ¢ 111/76 ο ο · ο · ο · 4 3 2 · 5 6 4 · 74 0781 1 ·-8 6 ο 々, Waizhuya (rare earth elements and The ratio of the Ca element mass to the total oxide conversion mass of the Ca element. * 2) "None: indicates that it has not been detected by the χ RD measurement, and" yes "indicates that it has been detected." However, Ca components such as Ca0 are not present in the abrasive material particles. ※ The total mass of the abrasive material 荥 solution has the added word ion (c mass ratio of "c", "-" means that no feed ion is added to the slurry. From the results shown in Table 2, it can be seen that ,,, ^ IV. / L Even in the grinding materials of the specified quality of 咼, 方 emulsified 钸 emulsified 钸 as the main component of rare earth oxygen-soluble (complete solid solution) oxide Gu Ya Lihua is about U π in the powder of No. ^ group formed by the Jin series grinding material, is the grinding material of the younger brother, compared with oxygen, has excellent grinding surface accuracy. Research materials 3rd money: second -Step description is related to another embodiment. This apricot application form is not only in the rare earth oxides, but also vulcanized and emulsified. 3] 6680 22 200535098 / Titanium oxide solid solution made of rhenium-based abrasive.
在本實施形態中,首弁I 能οπ 无,、罘1貫施形態或第2實施形 心同桉地,準備200克/升之肖 、ν> ϋ ,、,,a、 心A &鈽水溶液、硝酸鑭水溶 /夜、确&L錯水 >谷液及;ς肖酸辑.、、六 $ Κ,合液。鉍而,除此等外,尚 使硝酸鍅(硝酸氧化鍅)二水人彡 本田 、 义σ物〉谷解於純水中而以過濾除 去異物後’進一步加入έψ太而ιν ^ ,、尺而u乳化物換算質量調製200 克/升之硝酸氧化鍅水溶液。In this embodiment, the first 弁 I can be ππ, 罘 1, and the second embodiment is the same as in the second embodiment, and prepares 200 g / L of xiao, ν > ϋ ,,,, a, heart A &钸 Aqueous solution, lanthanum nitrate water-soluble / night, definite & L wrong water > grain fluid and ς Xiao acid series., Six $ K, liquid. In addition to bismuth, ytterbium nitrate (thionium oxide nitrate), dihydrate, manganese, Honda, sigma> gluten solution in pure water and filtered to remove foreign matter ', further added έ 太 而 ν ν ^,, On the other hand, the emulsion conversion mass of u prepared a 200 g / l aqueous solution of osmium nitrate oxide.
在本實施例中係將所準備之硝酸飾水溶液 3〇〇m卜輕鑭水料1G5nU、硝酸镨水溶液·、石肖酸妈 水溶液i5ml及石肖酸錯水溶液45ml混合,進一步加入純水 而得到3升之混合液(參照步驟i、第i圖)。此混合液中 所含有的各稀土族元素、㉖及鍅的氧化物換算質量之比例 為 60 : 21 : 7 : 3 : 9 〇Ce〇2 ·· La2〇3 ·· pr6〇n : Ca〇 : Zr〇2)。 步驟1之後的步驟係與第丨實施形態相同。得到平均粒徑 3.9//Π1之研磨材。 五:此等實施例係與實施例丨Q在硝酸鈽水溶 液等各水溶液之混合比例相異。在各實施例之混合比例係 如表3所示般。此以外之條件係與實施例1 〇相同。 :在本實施例中,係準備2個塑膠容器(容量均 為1 〇〇m 1 )’在各塑膠容器中,分別添加實施例1 〇所得到 之研磨材所分取的2Og研磨材、粒徑〇· 8nim的氧化鍅粒子 36〇g、1質量%之結晶纖維素(製品名:Avi cei,旭化成公司 製)水溶液l〇ml、1質量%之六偏磷酸鈉水溶液l〇ml與純水 20ml而使用漆料振盪器進行濕式混合粉碎研磨材3小時。 316680 200535098 得到之混合物使用3G筛目(網眼叫m)的 矛、乳化錯粒子後,得到研磨材漿液。繼而,於 到之研磨材聚液中加入純水,調製研磨材佔裝液全 :為10質量%的研磨材衆液。又,研磨試驗 二才將 均粒n “例寻相同為ο.1升。可得到平 刁粒仫2. 0// m的研磨材。 此等實施例’係與實施例15 =於2個_容器的研磨材相異。在實施例 研磨材。在實施例17中係 =研A在實施例18中係使用一 材。繼而,所使用之二二“例14所得到的研磨 15相同… 的種類以外的條件係與實施例 j f付到之研磨材的平均粒徑如表3所示般。 此等比較例係與實施例15即混合狀態令 口 矢兀素的氧化物換算質量之比例相显。夂比較例 中之混合比例如砉, 、谷比季乂例 相同m 所不。此以外的條件係與實施例】5 到之研磨材的平均粒徑如表3所示般。 比較例係與實施例15之合成時之授掉速度 ,…、貝苑例1的步驟2)相 此以外的條件係Mm /、縣速度為15〇rpm。 “的研磨材/、,彳15相同。可得到平均粒徑U7 在本實施例中 各水溶液之中,首春」心方、弟3貫施形態最初所準備之 液·卜二;容液3咖、硝'酸綱水溶 合/夜35n]1、硝酸鈣水溶液15ml混合, 316680 24 200535098In this example, the prepared nitric acid aqueous solution of 300 m light lanthanum water material 1G5nU, osmium nitrate aqueous solution, i5 ml of shi Xiao acid aqueous solution and 45 ml of shi Xiao acid aqueous solution were mixed, and pure water was further added to obtain 3 liters of mixed solution (see steps i, i). The ratio of the oxide-equivalent mass of each rare earth element, scandium, and scandium contained in this mixed solution is 60: 21: 7: 3: 9 〇Ce〇2 ·· La2〇3 ·· pr6〇n: Ca〇: Zr02). The steps after step 1 are the same as those in the first embodiment. An abrasive having an average particle diameter of 3.9 // Π1 was obtained. Fifth, these embodiments are different from the mixing ratio of each aqueous solution such as the embodiment Q in the thallium nitrate aqueous solution. The mixing ratio in each example is shown in Table 3. Other conditions are the same as in Example 10. : In this embodiment, two plastic containers (both with a capacity of 100 m 1) are prepared. In each plastic container, 20 g of the abrasive material and the granules obtained from the abrasive material obtained in Example 10 are separately added. 30.8 g of osmium oxide particles with a diameter of 0.8 nm, 10 ml of a 1% by mass aqueous solution of crystalline cellulose (product name: Aviceei, manufactured by Asahi Kasei Corporation), 10 ml of a 1% by mass aqueous solution of sodium hexametaphosphate and pure water 20 ml and wet-mixed pulverized abrasive using a paint shaker for 3 hours. 316680 200535098 After using the 3G sieve (mesh name m) to spear and emulsify the wrong particles, the abrasive slurry was obtained. Then, pure water was added to the obtained abrasive liquid to prepare a total of 10% by mass of abrasive liquid in the abrasive liquid. In addition, in the second grinding test, the average grain size n was equal to ο. 1 liter. Ping Diao grain size 2. 0 // m of abrasive material can be obtained. These examples' are the same as those of Example 15 = 2 _The grinding material of the container is different. In the example, the grinding material. In Example 17, the system = ken A uses one material in Example 18. Then, the second and second "milling 15 obtained in Example 14 are the same ... The conditions other than the type are as shown in Table 3 with the average particle diameter of the abrasive material provided in Example jf. These comparative examples show a significant proportion of the oxide-based mass of Example 15 in a mixed state. The mixing ratios in the 砉 comparative examples, such as 砉, 谷, and the trough season, are the same as m. The conditions other than this are as shown in Table 3 below. The comparative example is the same as in Example 15 when the speed was reduced, step 2) of Beiyuan Example 1 and other conditions were Mm /, and the county speed was 150 rpm. "The abrasive material is the same as that of 彳 15. The average particle size U7 can be obtained. Among the various aqueous solutions in this example, the first spring" is the liquid prepared by Xinfang and Di3. Coffee, nitrate's water-soluble / night 35n] 1, 15ml calcium nitrate aqueous solution mixed, 316680 24 200535098
St純水而得到2. 7升之混合液A。此混合液A中 60: 21 :二稀广族元素、及鈣的氧化物換算質量之比例為 A外’另外進供(=Ce〇2: U2〇3: ΡΓ6〇":⑽)。又,混合液 得到"1 鍅水溶液制,進一步再加入純水而 的二St溶液B (步驟U。此混合㈣所含有之錯 液Β之她、夜Γ貝里為9克。進一步相對於混合液Α與水溶 度鄭升Γ。^備1在2倍#量的碳酸氫銨水溶液2升(濃 面攪拌先!^ ,在㈣狀態之魏氫料溶液中,一 鹽的共沈:::,:t液A的全量、一面滴下而得到含碳酸 法,使水、、” R ^驟2)。其後’以與混合液“目同之方 氫銨水溶;Γ中V:入於含碳酸鹽的共沈殺粒子存在之碳酸 滴下時之η/Γ到含錯成分的沈殺之懸濁液(步驟3)。 貝k度為5〇mI/分。其次,使含有丑沈、:r教子 =成分的沈激物之懸濁液在室溫下㈣γ牛 稀釋熟成後之懸濁液至叫靜置 小蚪而使共沈澱粒子沈澱(步驟5)。靜置德 '隹 >/、後,使用陶莞洗淨裝置而進行洗淨(步驟7 \ 洗牙中,進行洗淨至懸濁液中之石肖 - 下。洗淨後,過遽含細粒子之水、容液為2〇_以 子的滤餅(步驟δ)。 子之水岭液而传到共沈殿粒 然後:以熱風乾燥機(熱風溫度】2〇t ’、打)乾燥所得到之濾餅(步驟9 ),敲碎 / B。 (步驟1 0 )。以+今泸徜η γ 于到之乾燥品 以㈣爐使一品進行锻燒(锻燒溫度_ 316680 25 200535098 °C、鍛燒時間3小時)(步驟n)。敲碎鍛燒品(步驟a)。 使所敲碑之鍛燒品以電氣爐(焙燒溫度9〇〇艺、焙燒時間3 J日守)焙燒(步驟13)。敲碎锻燒品(步驟14 )。得到^ 物固溶體(稀土族元素_Ca_Zr複合氧化物)之粉末。繼而匕 在所準備之2個塑膠容器(容量均為1〇〇ml)中,分別添’ 加攸所付到之氧化物固溶體分取者2〇g、粒徑〇· 8咖的 化鉛粒子360g、1質量%之Avicel水溶液1〇ml、i質量羊% §之=,礙酸鈉水溶液10ml與純水2〇ml而使用漆料振 進仃濕式混合粉碎氧化物固溶體3小時(步驟丨5 )。其後, 從所得到之混合物使用3〇篩目(網眼5〇〇#m)的篩子除 去氧化锆粒子後,得到研磨材漿液(氧化物固溶體漿液)于 J步驟16)。繼而’於所得到之研磨材漿液中加入純水, 週製漿液全體占有之研磨材的比例為10質量%的研磨材榮 液(步驟17)。又,研磨試驗中之研磨材漿液的使用量係 $其他之實施例等相同為。升。所得到之研磨材平均粒 i 為 1. 8 // m。 、—對於上述實施例10至19及比較例13至16的研磨材 進仃上述XRD測定而評估Ca〇之有無(參照表。此等之 中,將有關實施例15、比較例15及比較例16的研磨材之 咖圖譜表示於圖4中。對於上述實施例1〇至19及比較 例13至16的研磨材進行上述研磨試驗而評估研磨面精产 及研磨速度。結果如表3所示般。又,為在研磨試驗中: 研磨材漿液的調製方法,但在實施例1〇至14所得到的研 磨材係與第1實施形態之各實施例相同。在實施例】5至 316680 26 200535098 19及比k例13至1 6中係直接將最後所調製之研磨材漿液 用於研磨試驗。 如第4圖所示般,全部之研磨材的XRD圖譜係於28 3 (2 Θ )附近、及於3 2 · 5。附近出現譜峰。此等之譜峰 ί丁、表不立方晶氧化鈽的存在。繼而,在比較例之研磨材的 XRD圖譜於31.4。Ρ付近及45.〇。附近出現實施例之研磨材 相η ί見之°曰峰此等之譜峰係表示錯氧化物(與CaZr〇3 # ^ 9Q義)存在之°日夸。在比較例16之研磨材的XRD圖譜 二 =附近、34.5。附近…附 研磨z材中未出現之譜峰。此等之譜峰亦表示 Ce~Zr相同定義)存在之譜峰。 如此之XRD測定的結果可知, 為首之各實施例的研磨材中,係原料中^例=的研磨材 王部完全固溶於稀土族氧化物中一=及結兀素 之譜峰出玥仁在顯不鍅氧化物存在 ’出現的比較例15、16的 不完全,而以鍅氧化物出現於研磨錯疋素的固溶 (參照表3之純有無之欄)。4子之外側的狀態存在 316680 27 200535098 I-1 3 表St pure water to obtain 2.7 liters of mixed liquid A. In this mixed liquid A, the ratio of 60:21: two rare-earth elements and calcium oxide-equivalent mass ratio is supplied outside A 'and supplied separately (= Ce〇2: U2〇3: ΡΓ6〇 ": ⑽). In addition, the mixed solution is obtained from "1" aqueous solution, and further added with pure water is the two St solution B (step U. The mixed solution B contains 9 g of the mixed solution B, which is 9 g. It is further relative to The solubility of the mixed solution A and the water was positively raised. ^ Preparation 1 2 liters of 2 liters of ammonium bicarbonate aqueous solution 2 liters (concentrated surface stirring first! ^, In the Wei state of the hydrogen material solution, co-precipitation of a salt :: :,: The entire amount of liquid A was dropped to obtain a carbonic acid-containing method, and water was used to make "R ^ step 2). After that, it was dissolved in water with the same solution as" paraquat ammonium hydroxide; Γ in V: into Η / Γ at the time when the carbonic acid containing the co-precipitating particles containing carbonic acid is dripped to the suspension containing the wrong component (step 3). The k-degree is 50 mI / min. Secondly, : r 子 子 = The suspension of the stimulant of the ingredients at room temperature ㈣ γ bovine diluted the matured suspension to a standing maggot to precipitate co-precipitated particles (step 5). Let it stand '隹 > / 、 After that, use a Taowan washing device to wash (Step 7 \ In the tooth washing, wash to the bottom of the stone in the suspension. After washing, rinse with water and liquid containing fine particles. For 2 _Yizi's filter cake (step δ). The Ziling's water solution is passed to Gongshendian granules and then: the obtained filter cake is dried with a hot air dryer (hot air temperature) 20t ', beat (Step 9), Broken / B. (Step 10). Use one of the dried products + + 泸 徜 泸 徜 η γ to calcinate one product in the oven (calcination temperature_ 316680 25 200535098 ° C, calcination time 3 hours) (step n). Shatter the calcined product (step a). Rotate the calcined product of the tombstone in an electric furnace (baking temperature 900 ° C, firing time 3 J Nishou) (step 13). Shatter the calcined product (Step 14). A powder of a solid solution (rare earth element _Ca_Zr composite oxide) is obtained. Then, two plastic containers (capacity: 100 ml) are prepared, respectively, and added. The paid oxide solid solution was divided into 20 g, 360 g of lead particles with a diameter of 0.8 g, 10 ml of 1% by mass Avicel aqueous solution, and 10% by mass of sheep. § of = 10 ml and 20 ml of pure water were mixed into a wet-mixed pulverized oxide solid solution using a paint shaker for 3 hours (step 5). Thereafter, a 30 sieve was used from the obtained mixture. (Mesh 500 # m) in the sieve to remove the zirconia particles, to obtain a grinding material slurry (oxide solid solution slurry) in J step 16). Then, add pure water to the obtained grinding material slurry, weekly The proportion of the abrasives held by the slurry as a whole is 10% by mass (step 17). The amount of abrasive slurry used in the grinding test is the same as in the other examples. Liter. The average grain i of the abrasive material was 1.8 m.-For the abrasive materials of Examples 10 to 19 and Comparative Examples 13 to 16, the above XRD measurement was performed to evaluate the presence or absence of Ca0 (see table). Among them, the coffee charts of the abrasive materials of Example 15, Comparative Example 15 and Comparative Example 16 are shown in Fig. 4. The above-mentioned polishing tests were performed on the polishing materials of Examples 10 to 19 and Comparative Examples 13 to 16 to evaluate the polished surface finish and polishing rate. The results are shown in Table 3. In the polishing test, the method for preparing the slurry of the abrasive material was used. The abrasive materials obtained in Examples 10 to 14 were the same as those in the first embodiment. In Examples] 5 to 316680 26 200535098 19 and Comparative Examples 13 to 16 the last prepared grinding material slurry was directly used for the grinding test. As shown in FIG. 4, the XRD patterns of all the abrasives are in the vicinity of 28 3 (2 Θ) and in 3 2 · 5. Spectral peaks appear nearby. The peaks of these spectra indicate the existence of cubic crystals of hafnium oxide. Then, the XRD pattern of the abrasive in the comparative example was 31.4. P pays close to 45.〇. The abrasive material phases of the examples appear nearby. The peaks of these spectrums indicate the existence of mismatch oxides (as CaZr〇3 # ^ 9Q). The XRD pattern of the abrasive in Comparative Example 16 was 2 = near, 34.5. Nearby ... Attached spectrum peaks not appearing in the ground z material. These peaks also indicate the peaks with the same definition as Ce ~ Zr). According to the results of the XRD measurement, it can be known that among the abrasive materials of the first examples, the raw material of the raw material is ^ Example = the king of the abrasive material is completely solid-dissolved in the rare earth oxides-and the peak of the spectrum of the element is the coix kernel. Comparative examples 15 and 16 in which the presence of the presence of tritium oxide appears incomplete, and the tritium oxide appears in the solid solution of the millin (refer to the column of pure presence or absence in Table 3). There are states outside the 4th child 316680 27 200535098 I-1 3 Table
實施 例/比 較例 ※ 1) 原 料 中 之 Ca 成 分 (重 量 %) X 2) 原料 中之 Zr成 分 (重 量0/〇 鈽系研磨材 > 組成(w t %) 平 均 粒 徑 DdO (β m) TRE 0 (重 量 %) 3) CaO 之 有 無 % 3) ZrO 2之 有 無 TREO中之各豨土族氧 化物的含有率(重量 %) CeO 2 LS2 〇3 Prc On Nd2 〇3 實]0 2.14 6.663 87.99 68.19 23.86 7.94 0.02 無 無 3.88^ 實η 2.221 93. 98 63.84 28.73 7.42 0.02 無 無 3.61 _ 實12 5.182 89.99 66.67 25.56 7.76 0.02 無 無 4.03 ^ 實13 8. 884 84. 99 70.59 21.18 8.21 0.02 無 無 3.44 ^ 實14 11.105 81. 99 73.18 18.29 8.52 0.02 無 無 3.63〆 實15 2.144 6· 663 87. 99 68.19 23· 86 7. 94 0.02 無 無 2. 01_ 實16 2.221 93.98 63.84 28.73 7.42 0.02 無 無 1.69 一 實17 5.182 89.99 66.67 25.56 7.76 0.02 無 無 1.74_ 實18 8.884 84.99 70.59 21.18 8.21 0.02 無 無 2· 13_, 實19 11.105 81.99 73.18 18.29 8. 52 0.02 無 無 1·92_. tbl3 2.144 14. 806 76.98 77. 93 12.99 19. 06 0. 02 無 卜無 1.77 · 比14 18.507 71.99 83.34 6.95 9. 70 0. 02 無 無 1.68 . 比15 2.144 6.663 87.99 68.19 23.86 7. 94 0.02 無 有 L67_. 比16 2.144 6.663 87. 99 68.19 23.86 7.94 0.02 無 有 1.78 磨漿中 比 研材浪之ca的例Γ耋 性 特 磨 研 研磨面精度Rac埃 研磨速度c #111/分Examples / Comparative Examples * 1) Ca component (wt%) in raw materials X 2) Zr component (wt. 0 / 〇 钸 series abrasives > composition) in raw materials Composition (wt%) Average particle diameter DdO (β m) TRE 0 (% by weight) 3) Presence or absence of CaO% 3) Presence or absence of ZrO 2 in each TREO oxide (% by weight) CeO 2 LS2 〇3 Prc On Nd2 〇3 Real] 0 2.14 6.663 87.99 68.19 23.86 7.94 0.02 No No 3.88 ^ Real η 2.221 93. 98 63.84 28.73 7.42 0.02 No No 3.61 _ No 12 5.182 89.99 66.67 25.56 7.76 0.02 No No 4.03 ^ Real 13 8. 884 84. 99 70.59 21.18 8.21 0.02 No No 3.44 ^ Real 14 11.105 81. 99 73.18 18.29 8.52 0.02 No No 3.63 Real 15 2.144 6 · 663 87. 99 68.19 23 · 86 7. 94 0.02 No No 2. 01_ Real 16 2.221 93.98 63.84 28.73 7.42 0.02 No No 1.69 One Real 17 5.182 89.99 66.67 25.56 7.76 0.02 None None 1.74_ Real 18 8.884 84.99 70.59 21.18 8.21 0.02 None None 2. 13_, Real 19 11.105 81.99 73.18 18.29 8. 52 0.02 None None 1.92_. Tbl3 2.144 14. 806 76.98 77. 93 12.99 19. 06 0. 02 Wu Bu Wu 1.77 71.99 83.34 6.95 9. 70 0. 02 none without 1.68. Ratio 15 2.144 6.663 87.99 68.19 23.86 7. 94 0.02 without L67_. Ratio 16 2.144 6.663 87. 99 68.19 23.86 7.94 0.02 without 1.78 Example of ca Γ Rigid special grinding surface accuracy Rac Angular grinding speed c # 111 / min
Φ 2 ο· I 8 91 2· 86 6 5 一 2· 87 2· 5.815Γ〇Γ 20 ο· 250Φ 2 ο · I 8 91 2 · 86 6 5-2 · 87 2 · 5.815Γ〇Γ 20 ο · 250
4 L23I 2 7 05 - υι υ》1 )相對於原料中之稀土族元素、及Zr元素之總氧化 物換异質量的Ca元素質量之比例。 》2)相對於原料中之稀土族元素、^及元素之總氧化 物換算質量的Zr元素質量之比例。 X 3)「無」係表示未被xRD測定檢測出,「有」係表示檢測 出’—」係於原料中未添加Ca或Zr,而於研磨材粒子中 CaO或Zr〇2等之成分未存在。 ※4 )研磨材漿液之總質量占有的已添加之鈣離子() 之質夏比率,「―」係表示於漿液中未添加鈣離子。 如表3所示般,實施例1〇至19之研磨材係鈣元 0.16' 316680 28 200535098 於稀土族氧化物中完全者,⑽測定之結果, Γ::: :化舞及氧化錯。繼而,實施腳至19之研磨 π 〃、第1 λ施恶樣之各實施例之研磨材比較,具有相 :、J磨面知度且具有更高之研磨速度。此結果可知,由 氧化鈽作為主成分的稀土族氧化物中不僅與元素,锆 :右,被固溶之氧化物固溶體粉末所成之飾系研磨材,係 m ^的研磨面精度以及具有高的研磨速度之優異者。實 二1爭丨?9之研磨材係平均粒徑較實施例】°至14之研 =固面精度優。此結果可知,飼元素及錯元 磨面4生Γ凡王^ ’平均粒輕小之氧化物固溶體粒子者乃研 廇面釦度優且適宜作為研磨材。 A實施例13、14之研磨材係氧化鍅元素之比例較上述實 =例之研磨材更高的研磨材,但XRD測定之結果,在任一 :之:亦無檢測出氧化妈及氧化錯。因此,推斷舞元素及 於稀土族氧化物之固溶係报完全。但研磨面精度較 之研磨材差。此理未必明確’而若於稀土族氧化物 :兀素過剩地固溶’稀土族氧化物之結晶的結晶性合 大中田地降低,研磨面精度等研磨特性會降低。 二 過剩地固溶,較只㈣元素固溶時所得到之缺氧量二τ' 低,因此研磨面精度等研磨特性會降低。 牛 進-步’比較例15、16之研磨材係錯元 完全者,XRD測定之結果,在比較例15 二為不4 L23I 2 7 05-υιυ》 1) The ratio of Ca element mass to the total oxide exchange mass of rare earth elements and Zr element in the raw material. 》 2) The ratio of the mass of the Zr element to the total oxide-converted mass of the rare earth element, ^, and element in the raw material. X 3) "None" means that it was not detected by xRD measurement, "Yes" means that "-" was detected. No Ca or Zr was added to the raw materials, and components such as CaO or Zr〇2 were not added to the abrasive particles. presence. * 4) The mass-to-sum ratio of calcium ions () added to the total mass of the abrasive slurry, "-" indicates that no calcium ions were added to the slurry. As shown in Table 3, the abrasive materials of Examples 10 to 19 were calcium elements 0.16 '316680 28 200535098, which were completely in the rare earth oxides. As a result of the determination of Γ, Γ :::: chemical dance and oxidation errors. Then, compared with the grinding materials of each of the embodiments where the grinding of the feet to 19 was performed, π 第, and the first lambda application, the grinding materials had a better grinding speed and higher grinding speed. This result shows that the rare earth oxides containing hafnium oxide as the main component are not only related to the element, zirconium: right, decorative abrasives made of solid solution oxide solid solution powder, the polishing surface accuracy of m ^, and Excellent with high grinding speed. Real 2 1 struggle? The average particle size of the abrasive material of 9 is larger than that of the embodiment] ° to 14 = excellent solid surface accuracy. From this result, it can be seen that feed elements and staggered ground noodles have a high average particle size and small oxide solid solution particles, and are suitable for use as abrasives. The abrasive materials of Examples 13 and 14 were higher in the ratio of erbium oxide than the abrasive materials of the above examples. However, the results of XRD measurement showed that either: No oxide oxide or oxidation error was detected. Therefore, it is inferred that the elemental solution and the solid solution system of the rare earth oxides are complete. However, the accuracy of the polished surface is inferior to that of the abrasive. The reason is not necessarily clear, but if the crystallinity of the crystals of the rare earth oxides: solid solution excessively dissolved in the rare earth oxides, the crystallinity of the rare earth oxides is reduced, and polishing characteristics such as the accuracy of the polished surface are reduced. 2 Excess solid solution, lower than the amount of oxygen deficiencies τ 'obtained when only rhenium element is dissolved, so the polishing characteristics such as the accuracy of the polishing surface will be reduced. Niu Jin-step ’The abrasive materials of Comparative Examples 15 and 16 are completely incomplete, and the results of XRD measurement are in Comparative Example 15
CaZr〇3同定義)被檢測出,而在比較例16中別自、生:與 (與Ce-Zr複合氧化物同定義)被檢測 j,氧化物 骚者,此等之 316680 29 200535098 比較例的研磨材係研磨面精度及研磨速度之任一者均較實 施例的研磨材差。 從此結果可知,當製造使鈣元素之外進一步亦使錘元 素固〉谷於稀土族氧化物中之鈽系研磨材時,研磨材宜使妈 兀素及鍅兀素完全固溶,且研磨粒子(氧化物固溶體粒子) 之外不出現氧化鈣或氧化锆者,於研磨材之總氧化物換算 負里占有的錯兀素質量之比例宜為0· 01質量%至15質量%。 [i實施览复··在本實施形態中係說明有關研究本發明之 氧化物固溶體的觸媒特性的結果。觸媒特性係調查氧貯存 脫離此(0SC )與Ν〇χ吸附種/吸附能。又,測定試樣係使 用表4所示之氧化物固溶體。表4中之實施例9及比較例 12係與第2實施形態所使用之研磨材為相同的粉末。表4 中之實施例2G係依上述第!實施形態所說明之方法來製造 者0 [表4 ]CaZr〇3 (with the same definition) was detected, but in Comparative Example 16, it was not self-generating: and (with the same definition as Ce-Zr composite oxide) was detected. J, oxide, those 316680 29 200535098 Comparative Example Both the polishing surface accuracy and the polishing speed of the polishing material are inferior to those of the polishing material of the examples. From this result, it can be known that when manufacturing a rhenium-based abrasive material that further solidifies the hammer element in addition to the calcium element and is in the rare earth oxides, the abrasive material should be completely solid-soluble and the particles are abrasive. (Oxide solid solution particles) If calcium oxide or zirconium oxide does not appear, the proportion of the mass of the malococene in the total oxide conversion negative of the abrasive material is preferably 0.01% by mass to 15% by mass. [i Implementation Overview ... In this embodiment, the results of studying the catalyst characteristics of the oxide solid solution of the present invention will be described. The catalyst characteristics were investigated by oxygen storage (OSC) and NOx adsorption species / adsorption energy. For the measurement sample, an oxide solid solution shown in Table 4 was used. Example 9 and Comparative Example 12 in Table 4 are the same powders as the abrasives used in the second embodiment. Example 2G in Table 4 is based on the above! Producer 0 according to the method described in the embodiment [Table 4]
糸1)相 物換算質量的Ca元素質量之比例 条2 )相對於原料中之稀土族元素 物換算質量的Zr元素質量之比例 ----1 ~~ Ca及Zr元素之總氧化糸 1) Proportion of Ca element mass in phase conversion mass Article 2) Proportion of Zr element mass in relation to rare earth element conversion mass in raw material ---- 1 ~~ Total oxidation of Ca and Zr elements
Ca及Zr元素之總氧化 30 316680 200535098 ※3 )「無」係表示未被χ R D測定檢測出,「有」係表示檢測 出,「-」係於原料中未添加Ca*Zr,而於研磨材粒子中 CaO或Zr〇2等之成分未存在。 紐存㈣A :此氧貯存脫離能係就測定試樣量0.025± 0. OOlg而σ而藉熱傳導度檢測器測定。測定溫度為4〇〇 至8〇〇°C (每1〇〇t:),使用He作為載體氣體,脈衝(pulse) 大J 乂 1. 79mL進行。具體之測定順序係首先,於8〇 q。〇、 20〇CCm,He中保持測定試樣1〇分鐘後,降至最低測定溫 度( 400°C)。I盧而,形成各測定溫度後,將&脈衝導入4 根以上、He脈衝及&脈衝交互地導入4根以上。8〇〇1埶 處理係只最初進行,從低溫側之·。c依序朝高溫度側之 ,定溫度進行測^。氧貯存脫離能(⑽c)之評估方法係以 最初之脈衝作為標準,而從⑴脈衝及⑴脈衝之交互脈 衝的大小之比算出氧貯存脫離能(3根之平均值)。其結果 表示於第5圖中。 在第5圖中係表示在各測定溫度中之氧貯存脫離能作 圖出來的圖形’但依此第5圖,以比較例12、實施例9、 貝例20之順序可看出氧貯存脫離能會提高。因此,若Total oxidation of Ca and Zr elements 30 316680 200535098 ※ 3) "None" means that it has not been detected by χ RD measurement, "Yes" means that it has been detected, "-" means that Ca * Zr has not been added to the raw material, and it is ground No component such as CaO or ZrO2 exists in the material particles. Niutan㈣A: This oxygen storage release energy is determined by measuring the sample amount of 0.025 ± 0. OOlg and σ by a thermal conductivity detector. The measurement temperature was 4,000 to 800 ° C (per 100t :), and He was used as a carrier gas with a pulse of J J 1. 79 mL. The specific measurement sequence was first performed at 80 q. After the measurement sample was held in 〇, 200 ° C, and He for 10 minutes, the temperature was reduced to the lowest measurement temperature (400 ° C). After each measurement temperature has been established, four or more & pulses are introduced, and four or more He pulses and & pulses are introduced alternately. The 8001 treatment was performed only initially, from the low temperature side. c Sequentially toward the high-temperature side, measure at a constant temperature ^. The evaluation method of oxygen storage detachment energy (⑽c) is based on the initial pulse as the standard, and the oxygen storage detachment energy (average of 3) is calculated from the ratio of the magnitude of the interactive pulses of the ⑴ pulse and the ⑴ pulse. The results are shown in Figure 5. The graph in FIG. 5 is a graph showing the oxygen storage detachment at various measurement temperatures. However, according to FIG. 5, the oxygen storage detachment can be seen in the order of Comparative Example 12, Example 9, and Example 20. Can improve. Therefore, if
Ca或Zr固溶於鈽氧化物中,可提高氧貯存脫離能。 NOx吸附種/ ¾ p付能ά μλ ^ ~ ~~k ·此Ν〇χ吸附種/吸附能係就測定試樣 里 5— 〇· 00〗g而3,而藉擴散反射光譜檢測器(DSR) 測定出(載體氣體He)。測定溫度為20(TC至500t (每1〇〇 °C ),檢測出擴散反射光错。首先,於6〇〇t、39〇ccm之Ca or Zr is solid-dissolved in osmium oxide, which can improve the oxygen storage and detachment energy. NOx adsorbed species / ¾ p 付 能 ά λ ^ ~ ~~ k · This NO × χadsorbed species / adsorption energy is determined in the sample by 5— 〇 · 00〗 g and 3, and by the diffusion reflection spectrum detector (DSR ) Measured (carrier gas He). The measurement temperature was 20 (TC to 500t (per 100 ° C)), and the diffuse reflection light error was detected. First, at 600t, 3900ccm.
He(〇2 5%)中保持測定試樣1〇分鐘後,降至各測定溫度。 316680 3] 200535098 繼而 之BG (背景)測定。其後 ,以各測疋溫度進行H e中 導入NO/ 〇2 ( 5% ) /He氣體後 Ί π . non . ^ 、J 疋在 lmin、2min、5min、 lOmin之DSR。在各測定溫度中 从里主_〜發β回 Τ 進行上述操作。所得到之 結果表不於弟6圖至第9圖中。 弟6圖至弟9圖中传麥+々 # ^ ^ A ^1 - ^ ,、表〇測定溫度中之吸收波長與 其強度的測疋結果。從繁G同 攸乐6 g至第9圖,在比較例12、實 轭例9、實施例20之全部中玎 中了規祭到N〇2之吸附種。依據 公知之吸附模型,檢討第6圖 151至弟9圖之結果,n〇2之吸附 形態為螫合(Che 1 at ins)妝能、* g ^狀心進一步吸附量之順位為比 較例12<實施例9〈實施例2〇。 此N〇x除去能力係就測定試樣量〇. 〇25± o.ooig而S ’ #熱傳導檢測器與質量分析計進行測定(載 體氣體He)。測定係在以流通之中,測定試樣6〇(rc、保 持ίο分鐘後,降溫至吸附溫度30{rc繼而,導入N〇/ 〇2 (5%) /He後,保持30分鐘,其後,切換成以之流通後, 鲁以HTC/ηπη昇溫至60(rc,測定脫離氣體。 其結果’在比較例12中,未能確認出N〇x之脫離。另 外’在實施例9中,可看出質量數3〇之氣體檢測,並確認 NO氣體之脫離。在實施例2〇中可看出質量數3〇與32之 氣體檢測,並確認N〇2氣體之脫離。 依以上之結果可知,若Ca或Zr固溶於鈽氧化物中, N0x之吸附特性會提高。 (產業上之利用可能性) 本發明之氧化物固溶體粉末係可使用來作為研磨材、 32 316680 200535098 觸媒擔體或紫外線吸收劑等。例如若使用來作為研磨材, 可以四的研磨面精度研磨玻璃基板的玻璃材,若使用來作 為=車用觸媒擔體等,可提供一種A/F之氣體控制特性或 氮氧化物的除去性能優異之觸媒擔體,若使用來作為於化 链料或塗料等所含有的紫外線吸收劑等各種紫外線吸收 釗,可提供具有高的紫外線吸收能之紫外線吸收劑。 【圖式簡單說明】 .第1圖係表示製造步驟之流程圖。 第2圖係有關第!實施形態之各例所得到的研磨材之 XRD圖譜。 第3圖係表示研磨材漿液中鈣元素的比例與研磨面精 度之關係圖。 第4圖係有關第3實施形態之各例所得到的研磨材之 XRD圖譜。 第5圖仏則定第4實施形態之氧貯存脫離能的結果圖。 春 帛6圖仏周查第4實施形態之Ν〇χ吸附種/吸附能的 DSR。 第7圖奋凋查第4實施形態之ΝΟχ吸附種/吸附能的 DSR。 第8圖奋"周查第4實施形態之ΝΟχ吸附種/吸附能的 DSR。 第9圖係調查第4實施形態之NOx吸附種/吸附能的 DSR。 33 316680After holding the measurement sample in He (0 2 5%) for 10 minutes, the temperature was lowered to each measurement temperature. 316680 3] 200535098 followed by BG (background) measurement. Thereafter, DSR of NO / 〇2 (5%) / He gas was introduced into He at each measured radon temperature, Ίπ.non. ^, J 疋 at 1min, 2min, 5min, and 10min. In each measurement temperature, the above operation is performed by sending back β to T. The results obtained are not shown in Figures 6-9. Figure 6 to Figure 9 pass the wheat + 々 # ^ ^ A ^ 1-^, Table 0 to determine the absorption wavelength in temperature and its measurement results. From Fan G Tongyoule 6 g to Fig. 9, the adsorption species of No. 2 to No. 2 were included in all of Comparative Example 12, Real Example 9, and Example 20. Based on the well-known adsorption model, review the results in Figures 151 to 9 of Figure 6. The adsorption form of n02 is Che 1 at ins, and the order of the further adsorption amount of * g ^ is the comparative example 12 & lt Example 9 <Example 20. The Nox removal ability is determined based on the measurement sample amount of 0.2525 o.ooig, and the S '# heat conduction detector and mass spectrometer are used for measurement (carrier gas He). The measurement system is in circulation. After the measurement sample is 60 ° C and held for ο minutes, the temperature is lowered to the adsorption temperature of 30 ° C. Then, No./〇2 (5%) / He is introduced, and then it is held for 30 minutes. After switching to circulation, Lu heated up to 60 ° C with HTC / ηπη, and measured the release gas. As a result, in Comparative Example 12, the release of Nox was not confirmed. In addition, in Example 9, It can be seen that the gas number of 30 is detected, and the desorption of NO gas can be confirmed. In Example 20, the gas detection of mass numbers 30 and 32 can be seen, and the desorption of No 2 gas can be confirmed. According to the results above It can be seen that if Ca or Zr is solid-dissolved in rhenium oxide, the adsorption characteristics of NOx will be improved. (Industrial application possibility) The oxide solid solution powder of the present invention can be used as an abrasive, 32 316680 200535098 contact Medium carrier, ultraviolet absorber, etc. For example, if it is used as a polishing material, the glass material of a glass substrate can be ground with a precision of four polishing surfaces. If it is used as a vehicle catalyst carrier, etc., an A / F Catalyst carrier with excellent gas control characteristics and nitrogen oxide removal performance If used as various UV absorbers such as UV absorbers contained in chemical materials or coatings, it can provide UV absorbers with high UV absorbing energy. [Brief description of the drawings]. Figure 1 shows manufacturing The flow chart of the steps. Fig. 2 is an XRD pattern of the abrasive material obtained in each example of the first embodiment. Fig. 3 is a graph showing the relationship between the ratio of calcium element in the abrasive material slurry and the accuracy of the abrasive surface. Fig. 4 This is an XRD pattern of the abrasive material obtained in each example of the third embodiment. Fig. 5 shows the results of the oxygen storage release energy of the fourth embodiment. Fig. 6 shows the results of weekly inspection of No. 4 of the fourth embodiment. DSR of x-adsorbed species / adsorption energy. Fig. 7 shows the DSR of the 4th embodiment of the χχ adsorption species / adsorption energy. Fig. 8 Fendi " Weekly check of DSR of the noble-adsorbed species / adsorption energy of the fourth embodiment. Figure 9 is a DSR that investigates the NOx adsorption species / adsorption energy of the fourth embodiment. 33 316680
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JP4185955B2 (en) * | 2006-01-27 | 2008-11-26 | 三井金属鉱業株式会社 | Oxygen scavenger and method for producing oxygen scavenger |
JP4210310B2 (en) * | 2006-06-29 | 2009-01-14 | 三井金属鉱業株式会社 | Dehumidification / deoxygenation method |
WO2008001745A1 (en) * | 2006-06-29 | 2008-01-03 | Mitsui Mining & Smelting Co., Ltd. | Dehumidifying/deoxidizing agent |
CN101568615B (en) * | 2006-12-28 | 2013-02-06 | 花王株式会社 | Polishing liquid composition |
WO2008140004A1 (en) * | 2007-05-10 | 2008-11-20 | Mitsui Mining & Smelting Co., Ltd. | Deoxidant and method for producing the same |
WO2010054054A2 (en) * | 2008-11-05 | 2010-05-14 | Wayne State University | Calcium and lanthanum solid base catalysts for transesterification |
WO2010118553A1 (en) | 2009-04-15 | 2010-10-21 | Rhodia (China) Co., Ltd. | A cerium-based particle composition and the preparation thereof |
JP5883609B2 (en) * | 2011-10-12 | 2016-03-15 | 一般財団法人ファインセラミックスセンター | Polishing material, polishing composition and polishing method |
CN102559064B (en) * | 2011-12-15 | 2014-01-29 | 上海华明高纳稀土新材料有限公司 | Cerium-zirconium praseodymium sosoloid and preparation method thereof |
JP5046259B1 (en) * | 2012-01-25 | 2012-10-10 | 公益財団法人三重県産業支援センター | Glass abrasive |
TWI561496B (en) * | 2012-04-05 | 2016-12-11 | China Steel Corp | Far-infrared emitting material and method of making the same |
CN103923603A (en) * | 2013-01-15 | 2014-07-16 | 安阳市岷山有色金属有限责任公司 | Oxide solid solution powder |
JP2015120844A (en) * | 2013-12-24 | 2015-07-02 | 旭硝子株式会社 | Polishing agent production method, polishing method, and semiconductor integrated circuit device production method |
CN105797706A (en) * | 2014-12-29 | 2016-07-27 | 北京有色金属研究总院 | Cerium-lanthanum solid solution catalyst for purifying diesel vehicle exhaust particles and preparation method thereof |
JP6738776B2 (en) * | 2017-08-01 | 2020-08-12 | 信越化学工業株式会社 | Silicone rubber composition |
JP7019379B2 (en) * | 2017-11-02 | 2022-02-15 | 花王株式会社 | Composite abrasive grains |
CN115724457A (en) * | 2022-12-05 | 2023-03-03 | 上海华明高纳稀土新材料有限公司 | White nano cerium oxide and preparation method thereof |
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FR2701472B1 (en) * | 1993-02-10 | 1995-05-24 | Rhone Poulenc Chimie | Process for the preparation of compositions based on mixed oxides of zirconium and cerium. |
JP3738454B2 (en) * | 1993-08-11 | 2006-01-25 | 住友化学株式会社 | Composite metal oxide powder and method for producing the same |
FR2736343B1 (en) * | 1995-07-03 | 1997-09-19 | Rhone Poulenc Chimie | COMPOSITION BASED ON ZIRCONIUM OXIDE AND CERIUM OXIDE, METHOD OF PREPARATION AND USE |
JPH10154523A (en) * | 1996-09-27 | 1998-06-09 | Tosoh Corp | Defective fluorite type ceria system solid electrolyte |
JP3995411B2 (en) * | 2000-11-24 | 2007-10-24 | 三井金属鉱業株式会社 | Method for producing cerium-based abrasive |
TW528796B (en) * | 2000-12-13 | 2003-04-21 | Mitsui Mining & Amp Smelting C | Cerium-based abrasive and method of evaluating the same |
US6770392B2 (en) * | 2001-04-27 | 2004-08-03 | Air Products And Chemicals, Inc. | Ceria based solid electrolytes |
CN1206028C (en) * | 2003-04-28 | 2005-06-15 | 华东理工大学 | Nano cerium-zirconium base compound oxide and preparation process thereof |
JP3917953B2 (en) * | 2003-06-11 | 2007-05-23 | セイミケミカル株式会社 | Light rare earth raw material for cerium abrasive production |
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JPWO2005070832A1 (en) | 2007-12-27 |
CN1764601A (en) | 2006-04-26 |
KR100706095B1 (en) | 2007-04-12 |
WO2005070832A1 (en) | 2005-08-04 |
EP1707534A1 (en) | 2006-10-04 |
TWI304791B (en) | 2009-01-01 |
CN100410176C (en) | 2008-08-13 |
KR20050109592A (en) | 2005-11-21 |
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